JPWO2017038195A1 - Moisture curable hot melt urethane composition, method for producing foamed cured product thereof, synthetic leather, and method for producing the same - Google Patents
Moisture curable hot melt urethane composition, method for producing foamed cured product thereof, synthetic leather, and method for producing the same Download PDFInfo
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- JPWO2017038195A1 JPWO2017038195A1 JP2016567271A JP2016567271A JPWO2017038195A1 JP WO2017038195 A1 JPWO2017038195 A1 JP WO2017038195A1 JP 2016567271 A JP2016567271 A JP 2016567271A JP 2016567271 A JP2016567271 A JP 2016567271A JP WO2017038195 A1 JPWO2017038195 A1 JP WO2017038195A1
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- melt urethane
- hot melt
- urethane prepolymer
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Abstract
本発明は、イソシアネート基を有するホットメルトウレタンプレポリマー(A)と、N,N’−ジニトロソペンタメチレンテトラミン(b1)、尿素(b2)、及びポリオール(b3)を含む発泡剤組成物(B)とを含有することを特徴とする湿気硬化型ホットメルトウレタン組成物を提供するものである。また、本発明は、前記ホットメルトウレタンプレポリマー(A)を加熱溶融した後に、前記発泡剤組成物(B)と混合して基材に塗布し、次いで、前記(A)の加熱溶融温度以上の温度で加熱処理をすることにより発泡硬化させることを特徴とする湿気硬化型ホットメルト組成物の発泡硬化物の製造方法を提供するものである。本発明が解決しようとする課題は、良好な風合いを有する発泡硬化物が得られ、薄膜でも良好な発泡状態を保持することができる、無溶剤の発泡システムを提供することである。The present invention relates to a foaming agent composition (B) comprising a hot melt urethane prepolymer (A) having an isocyanate group, N, N′-dinitrosopentamethylenetetramine (b1), urea (b2), and polyol (b3). And a moisture-curable hot-melt urethane composition. Further, in the present invention, the hot melt urethane prepolymer (A) is heated and melted, mixed with the foaming agent composition (B) and applied to a substrate, and then the heating and melting temperature of the (A) or higher. The present invention provides a method for producing a foam-cured product of a moisture-curing hot melt composition, wherein the foam-cured product is heat-treated at a temperature of 5%. The problem to be solved by the present invention is to provide a solventless foaming system in which a foamed cured product having a good texture can be obtained and a good foamed state can be maintained even in a thin film.
Description
本発明は、湿気硬化型ホットメルトウレタン組成物、その発泡硬化物の製造方法、合成皮革、及び、その製造方法を提供することである。 An object of the present invention is to provide a moisture curable hot melt urethane composition, a method for producing a foamed cured product thereof, a synthetic leather, and a method for producing the same.
欧州におけるジメチルホルムアミド(DMF)の使用規制が本格化される中、無溶剤で省エネルギーな環境対応型樹脂の供給が渇望されている。その中、無溶剤である湿気硬化型ホットメルトウレタン組成物が非常に注目されており、合成皮革、建築材料、自動車内装材、冷蔵庫、スマートフォン、パソコン、カーナビ等の電気電子機器などの製造において、広く利用されている。中でも、近年は緩衝効果による耐衝撃性や風合いの向上、湿気硬化型ホットメルトウレタン組成物の使用量低減等を目的に、湿気硬化型ホットメルトウレタン組成物を発泡させ、発泡硬化物とするケースが増えている。 As regulations on the use of dimethylformamide (DMF) in Europe are in full swing, the supply of environmentally friendly resins that are solvent-free and energy-saving is eagerly desired. Among them, a moisture-curable hot melt urethane composition that is solvent-free has attracted a great deal of attention, and in the manufacture of electrical and electronic equipment such as synthetic leather, building materials, automotive interior materials, refrigerators, smartphones, personal computers, car navigation systems, etc. Widely used. In particular, in recent years, a case where a moisture-curable hot-melt urethane composition is foamed to form a foam-cured product for the purpose of improving impact resistance and texture due to a buffering effect and reducing the amount of use of the moisture-curable hot-melt urethane composition. Is increasing.
前記湿気硬化型ホットメルトウレタン組成物を発泡硬化させる方法としては、水や水蒸気を使用した水発泡法が広く研究されている(例えば、特許文献1及び2を参照。)。この水発泡法は、水や水蒸気が湿気硬化型ホットメルトウレタンが有するイソシアネート基と反応して発生する炭酸ガスを泡として硬化物中に残存させるものである。また、この水発泡法では湿気硬化型ホットメルトウレタンと水分等とを強制撹拌することで、泡の発生率を高めること、及び強制撹拌時に巻き込む泡を積極的に残存させることが一般的である。 As a method for foam-curing the moisture-curable hot melt urethane composition, a water foaming method using water or water vapor has been widely studied (for example, see Patent Documents 1 and 2). In this water foaming method, carbon dioxide gas generated by the reaction of water or water vapor with the isocyanate group of the moisture-curable hot melt urethane is left as foam in the cured product. Further, in this water foaming method, it is common to forcibly stir the moisture-curing hot melt urethane and moisture to increase the generation rate of bubbles and to positively leave the bubbles involved during forced stirring. .
しかしながら、前記水発泡法では前記強制撹拌を行った際の系中の混合状態により発泡の度合いが異なるため、実験設備から生産設備へのスケールアップを図った際には、均一な発泡状態を有する発泡硬化物を、再現よく安定的に生産することが極めて困難であった。特に、前記水発泡法では、特に発泡硬化物の厚さを100μm未満の薄膜とする場合には、炭酸ガスが皮膜中から抜けてしまい、強制撹拌時の巻き込みにより発生した泡だけが残存するケースが多く、良好な発泡状態を再現よく安定的に形成できるよう設計することが極めて困難であった。 However, in the water foaming method, since the degree of foaming varies depending on the mixed state in the system when the forced stirring is performed, when the scale-up from the experimental equipment to the production equipment is attempted, it has a uniform foaming state. It was extremely difficult to stably produce a foam cured product with good reproducibility. In particular, in the water foaming method, particularly when the thickness of the foamed cured product is a thin film having a thickness of less than 100 μm, the carbon dioxide gas escapes from the film, and only bubbles generated by entrainment during forced stirring remain. Therefore, it has been extremely difficult to design so that a good foamed state can be stably formed with good reproducibility.
前記水発泡法以外の発泡方法としては、例えば、ケトオキシムでブロックされたウレタンプレポリマー、脂肪族ジアミン、熱膨張性微粒子、及びDMFを含有する組成物を加熱して発泡する方法が開示されている(例えば、特許文献3を参照。)。しかしながら、前記方法ではDMFを使用していることや、加熱温度が180℃程度と非常に高く、基材や基布への悪影響が考えられる。また、前記熱膨張性微粒子は加熱発泡後も固体状で硬いため、得られる発泡硬化物の風合いが悪いとの問題があった。 As a foaming method other than the water foaming method, for example, a method of heating and foaming a composition containing a urethane prepolymer blocked with ketoxime, an aliphatic diamine, thermally expandable fine particles, and DMF is disclosed. (For example, see Patent Document 3). However, in the above method, DMF is used and the heating temperature is as high as about 180 ° C., which may have an adverse effect on the base material and the base fabric. Further, since the thermally expandable fine particles are solid and hard even after heat foaming, there is a problem that the foamed cured product obtained has a poor texture.
一方、ポリウレタンの利用例として近年盛んに研究がなされている合成皮革は、一般的に、基布、中間層、及び表皮層を備え、車両内装材、家具、透湿防水衣料等の製造に広く利用されている。前記中間層としては、ポリウレタンのN,N−ジメチルホルムアミド(DMF)溶液を湿式加工法等により形成された発泡層あるいは多孔層として使用されることが一般的である。しかしながら、前記DMFは、前述の通り、欧州や中国での使用規制が本格化されており、合成皮革用途においても、その使用の低減化や無溶剤化への移行が急務となっている。 On the other hand, synthetic leather, which has been actively studied in recent years as an example of the use of polyurethane, generally comprises a base fabric, an intermediate layer, and a skin layer, and is widely used in the manufacture of vehicle interior materials, furniture, moisture-permeable waterproof clothing, and the like. It's being used. As the intermediate layer, an N, N-dimethylformamide (DMF) solution of polyurethane is generally used as a foamed layer or a porous layer formed by a wet processing method or the like. However, as described above, the regulations on the use of DMF are in full swing in Europe and China, and there is an urgent need to reduce the use and shift to solvent-free use in synthetic leather.
前記中間層を形成する際のDMF低減化方法としては、例えば、前述の特許文献3に記載されているような方法が開示されている。しかしながら、前記方法ではDMFの使用量が依然として多いことや、加熱温度が180℃程度と非常に高く、基布や離型紙などへの悪影響が考えられる。また、前記熱膨張性微粒子は加熱発泡後も固体状で硬いため、得られる合成皮革の風合いが悪いとの問題があった。 As a DMF reduction method for forming the intermediate layer, for example, a method as described in Patent Document 3 is disclosed. However, in the above method, the amount of DMF used is still large, and the heating temperature is as high as about 180 ° C., which may adversely affect the base fabric and release paper. Further, since the thermally expandable fine particles are solid and hard even after heating and foaming, there is a problem that the texture of the resultant synthetic leather is poor.
一方、中間層の形成にDMFを一切使用しない方法としては、例えば、前述の特許文献1及び2に記載されているような、水や水蒸気を使用した水発泡法が広く研究されている。しかしながら、前記水発泡法では前記強制撹拌を行った際の系中の混合状態により発泡の度合いが異なるため、実験設備から生産設備へのスケールアップを図った際には、均一な発泡状態を有する中間層を、再現よく安定的に生産することが極めて困難であった。また、前記水発泡法では、特に中間層の厚さを100μm未満の薄膜とする場合には、炭酸ガスが皮膜中から抜けてしまい、強制撹拌時の巻き込みにより発生した泡だけが残存するケースが多く、良好な発泡状態を再現よく安定的に形成できるよう設計することが極めて困難であった。 On the other hand, as a method of not using DMF at all for forming the intermediate layer, for example, a water foaming method using water or water vapor as described in Patent Documents 1 and 2 described above has been widely studied. However, in the water foaming method, since the degree of foaming varies depending on the mixed state in the system when the forced stirring is performed, when the scale-up from the experimental equipment to the production equipment is attempted, it has a uniform foaming state. It was extremely difficult to stably produce the intermediate layer with good reproducibility. In the water foaming method, particularly when the thickness of the intermediate layer is a thin film of less than 100 μm, carbon dioxide gas escapes from the film, and only bubbles generated by entrainment during forced stirring remain. In many cases, it has been extremely difficult to design such that a good foamed state can be stably formed with good reproducibility.
本発明が解決しようとする課題は、良好な風合いを有する発泡硬化物が得られ、薄膜でも良好な発泡状態を保持することができる、無溶剤の発泡システムを提供することである。 The problem to be solved by the present invention is to provide a solventless foaming system in which a foamed cured product having a good texture can be obtained and a good foamed state can be maintained even in a thin film.
本発明は、イソシアネート基を有するホットメルトウレタンプレポリマー(A)と、N,N’−ジニトロソペンタメチレンテトラミン(b1)、尿素(b2)、及びポリオール(b3)を含む発泡剤組成物(B)とを含有することを特徴とする湿気硬化型ホットメルトウレタン組成物を提供するものである。 The present invention relates to a foaming agent composition (B) comprising a hot melt urethane prepolymer (A) having an isocyanate group, N, N′-dinitrosopentamethylenetetramine (b1), urea (b2), and polyol (b3). And a moisture-curable hot-melt urethane composition.
また、本発明は、イソシアネート基を有するホットメルトウレタンプレポリマー(A)を加熱溶融した後に、N,N’−ジニトロソペンタメチレンテトラミン(b1)、尿素(b2)、及びポリオール(b3)を含む発泡剤組成物(B)と混合して基材に塗布し、次いで、前記ホットメルトウレタンプレポリマー(A)の加熱溶融温度以上の温度で加熱処理をすることにより発泡硬化させることを特徴とする湿気硬化型ホットメルトウレタン組成物の発泡硬化物の製造方法を提供するものである。 The present invention also includes N, N′-dinitrosopentamethylenetetramine (b1), urea (b2), and polyol (b3) after heating and melting the hot melt urethane prepolymer (A) having an isocyanate group. It is mixed with a foaming agent composition (B), applied to a substrate, and then foamed and cured by heat treatment at a temperature equal to or higher than the heat melting temperature of the hot melt urethane prepolymer (A). The present invention provides a method for producing a foam cured product of a moisture curable hot melt urethane composition.
また、本発明は、基布(i)、中間層(ii)、及び表皮層(iii)を有する合成皮革であって、前記中間層(ii)が、前記湿気硬化型ホットメルトウレタン組成物の発泡硬化物であることを特徴とする合成皮革を提供するものである。 The present invention also provides a synthetic leather having a base fabric (i), an intermediate layer (ii), and a skin layer (iii), wherein the intermediate layer (ii) is a moisture-curable hot melt urethane composition. The present invention provides a synthetic leather characterized by being a foam cured product.
更に、本発明は、イソシアネート基を有するホットメルトウレタンプレポリマー(A)を加熱溶融した後に、N,N’−ジニトロソペンタメチレンテトラミン(b1)、尿素(b2)、及びポリオール(b3)を含む発泡剤組成物(B)を混合して湿気硬化型ホットメルトウレタン組成物を得、前記湿気硬化型ホットメルト組成物を、離型紙上に形成した表皮層(iii)上に塗布し、次いで、前記ホットメルトウレタンプレポリマー(A)の加熱溶融温度以上の温度で加熱処理をすることにより中間層(ii)を形成し、次いで前記中間層(ii)上に基布(i)を貼り合せることを特徴とする合成皮革の製造方法を提供するものである。 Further, the present invention includes N, N′-dinitrosopentamethylenetetramine (b1), urea (b2), and polyol (b3) after the hot melt urethane prepolymer (A) having an isocyanate group is heated and melted. Mixing the foaming agent composition (B) to obtain a moisture curable hot melt urethane composition, applying the moisture curable hot melt composition on the skin layer (iii) formed on the release paper, The intermediate layer (ii) is formed by heat treatment at a temperature equal to or higher than the heating and melting temperature of the hot melt urethane prepolymer (A), and then the base fabric (i) is bonded onto the intermediate layer (ii). A synthetic leather production method characterized by the above is provided.
本発明の湿気硬化型ホットメルトウレタン組成物は、特定の熱分解性発泡剤を用いることにより、薄膜でも良好な発泡状態を保持することができ、良好な風合いを有する発泡硬化物が得られるものである。また、発泡後も発泡硬化物の機械的物性の低下を引き起こさないものである。また、水の影響を受けることなく発泡させることができ、湿気硬化型ホットメルトウレタン組成物が溶融状態から一度冷却固化した場合や湿気硬化途中でも、再度加熱処理することで熱分解性発泡剤による発泡を促進することができる。 The moisture-curable hot melt urethane composition of the present invention can maintain a good foamed state even in a thin film by using a specific thermally decomposable foaming agent, and a foamed cured product having a good texture can be obtained. It is. Further, even after foaming, the mechanical properties of the foamed cured product are not lowered. In addition, it can be foamed without being affected by water, and when the moisture-curable hot-melt urethane composition is once cooled and solidified from the melted state or in the course of moisture curing, it can be reheated to produce a heat-decomposable foaming agent. Foaming can be promoted.
また、本発明の合成皮革は、中間層の形成にDMF等の有機溶剤を一切使用しないものであるから、人体への悪影響が少ないものである。また、中間層の形成に特定の熱分解性発泡剤を用いることにより、中間層が薄膜である場合でも良好な発泡状態を保持することができ、良好な風合いを有する中間層及び合成皮革が得られる。 Further, the synthetic leather of the present invention does not use any organic solvent such as DMF for the formation of the intermediate layer, and therefore has little adverse effect on the human body. Further, by using a specific thermally decomposable foaming agent for forming the intermediate layer, it is possible to maintain a good foamed state even when the intermediate layer is a thin film, and to obtain an intermediate layer and a synthetic leather having a good texture. It is done.
本発明の湿気硬化型ホットメルトウレタン組成物は、イソシアネート基を有するホットメルトウレタンプレポリマー(A)と、N,N’−ジニトロソペンタメチレンテトラミン(b1)、尿素(b2)、及びポリオール(b3)を含む発泡剤組成物(B)とを必須成分として含有するものである。 The moisture-curable hot melt urethane composition of the present invention includes an isocyanate group-containing hot melt urethane prepolymer (A), N, N′-dinitrosopentamethylenetetramine (b1), urea (b2), and polyol (b3). ) Containing a blowing agent composition (B) as an essential component.
本発明においては、前記発泡剤組成物(B)として、N,N’−ジニトロソペンタメチレンテトラミン(b1)、尿素(b2)、及びポリオール(b3)を含有することが必須である。この特定の発泡剤組成物を用いることにより、発泡硬化物の機械的物性の低下を引き起こすことなく、良好な風合いを有する発泡硬化物が得られ、薄膜でも良好な発泡状態を保持することができる。また、水の影響を受けることなく発泡させることができ、湿気硬化型ホットメルトウレタン組成物が溶融状態から一度冷却固化した場合や湿気硬化途中でも、再度加熱処理することで発泡形成することができる。 In the present invention, it is essential that the blowing agent composition (B) contains N, N′-dinitrosopentamethylenetetramine (b1), urea (b2), and polyol (b3). By using this specific foaming agent composition, a foamed cured product having a good texture can be obtained without causing deterioration of the mechanical properties of the foamed cured product, and a good foamed state can be maintained even in a thin film. . Moreover, it can be foamed without being affected by water, and when the moisture-curable hot-melt urethane composition is once cooled and solidified from the melted state or in the course of moisture curing, it can be foamed by heating again. .
前記N,N’−ジニトロソペンタメチレンテトラミン(b1)は熱分解性発泡剤として機能するものである。前記(b1)は主に天然ゴムや合成ゴムの発泡剤として使用されるものであり、ガス発生量や分解時の発熱量が極めて大きいことが知られているため、加熱溶融状態で基材等に塗布され使用される湿気硬化型ホットメルトウレタン組成物に採用した場合、混合直後に熱分解することが想定されるため適合しないと思われた。しかしながら、湿気硬化型ホットメルトウレタン組成物に用いられる前記ホットメルトウレタンプレポリマー(A)は通常80〜120℃の温度で加熱溶融されるのに対し、前記(b1)はこの温度範囲以上の温度で加熱処理(以下、「後加熱」と略記する。)することで発泡し、薄膜でも良好な発泡状態を形成保持できることが分かった。この際、前記(b1)の熱分解後の成分が、前記ホットメルトウレタンプレポリマー(A)中のイソシアネート基と反応することで泡を固定化できたものと推測される。前記ホットメルトウレタンプレポリマー(A)の加熱溶融温度以上の温度領域でガス発生量が増大する熱分解性発泡剤は多数あるものの、前記(b1)以外の熱分解性発泡剤では、熱分解後の成分が前記ホットメルトウレタンプレポリマー(A)中のイソシアネート基と反応しないため泡の固定化が困難であり、得られる泡が硬化後に歪んだり潰れたりする場合があるため、得られる発泡硬化物の風合いが損なわれたり、凹凸により表面外観が損なわれるとの問題がある。 The N, N′-dinitrosopentamethylenetetramine (b1) functions as a thermally decomposable foaming agent. The (b1) is mainly used as a foaming agent for natural rubber and synthetic rubber, and is known to have a very large amount of gas generation and heat generation during decomposition. When it was applied to a moisture-curing hot melt urethane composition that was applied to and used, it was assumed that it was not suitable because it was assumed to thermally decompose immediately after mixing. However, the hot melt urethane prepolymer (A) used in the moisture curable hot melt urethane composition is usually heated and melted at a temperature of 80 to 120 ° C., whereas the (b1) is a temperature higher than this temperature range. It was found that foaming was performed by heat treatment (hereinafter abbreviated as “post-heating”), and a good foamed state could be formed and maintained even with a thin film. At this time, it is presumed that the component after thermal decomposition of (b1) reacted with the isocyanate group in the hot melt urethane prepolymer (A) to fix the bubbles. Although there are many thermally decomposable foaming agents that increase the amount of gas generation in the temperature range higher than the heating and melting temperature of the hot melt urethane prepolymer (A), in the thermally decomposable foaming agents other than (b1), Since the component of the above does not react with the isocyanate group in the hot melt urethane prepolymer (A), it is difficult to fix the foam, and the resulting foam may be distorted or crushed after curing. There is a problem that the texture of the surface is impaired, or the surface appearance is impaired by unevenness.
前記N,N’−ジニトロソペンタメチレンテトラミン(b1)の使用量としては、後加熱による良好な発泡状態を形成でき、発泡硬化物の機械的物性への悪影響が少ない点から、前記発泡剤組成物(B)中3〜50質量%の範囲であることが好ましく、5〜40質量%の範囲であることがより好ましい。 The amount of the N, N′-dinitrosopentamethylenetetramine (b1) used is that the foaming agent composition is capable of forming a good foamed state by post-heating and has little adverse effect on the mechanical properties of the foamed cured product. It is preferable that it is the range of 3-50 mass% in a thing (B), and it is more preferable that it is the range of 5-40 mass%.
前記尿素(b2)は前記(b1)の発泡助剤として機能するものである。前記尿素(b2)を用いない場合には、発泡はするものの泡が硬化後に歪んだり潰れたりする場合があったり、前記(b1)の発泡を制御できない場合があり、得られる発泡硬化物の風合いや表面外観が損なわれる。前記尿素(b2)の使用量としては、薄膜においても後加熱により良好な発泡状態を形成できる点から、前記発泡剤組成物(B)中3〜50質量%の範囲であることが好ましく、8〜40質量%の範囲であることがより好ましい。 The urea (b2) functions as a foaming aid for the (b1). When the urea (b2) is not used, foaming may be distorted or crushed after curing, or foaming of the (b1) may not be controlled. And the surface appearance is impaired. The amount of urea (b2) used is preferably in the range of 3 to 50% by mass in the foaming agent composition (B) from the viewpoint that a good foamed state can be formed by post-heating even in a thin film. More preferably, it is in the range of ˜40 mass%.
前記N,N’−ジニトロソペンタメチレンテトラミン(b1)と尿素(b2)との質量比[(b1)/(b2)]としては、薄膜においても後加熱による良好な発泡状態を形成できる点から、10/90〜90/10の範囲であることが好ましく、30/70〜70/30の範囲であることがより好ましい。 As the mass ratio [(b1) / (b2)] of the N, N′-dinitrosopentamethylenetetramine (b1) and urea (b2), it is possible to form a good foamed state by post-heating even in a thin film. The range is preferably 10/90 to 90/10, and more preferably 30/70 to 70/30.
前記ポリオール(b3)は、ビヒクルとして機能するものであり、前記(b1)及び(b2)を前記ホットメルトウレタンプレポリマー(A)中に均一に混合するために用いるものである。 The polyol (b3) functions as a vehicle and is used to uniformly mix the (b1) and (b2) into the hot melt urethane prepolymer (A).
前記ポリオール(b3)としては、例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、ポリアクリルポリオール、ポリオレフィンポリオール、ひまし油ポリオール、多価アルコール等;これらの共重合物などを用いることができる。これらのポリオールは、発泡硬化物が使用される用途に応じて適宜決定することができ、単独で用いても2種以上を併用してもよい。 Examples of the polyol (b3) include polyester polyols, polyether polyols, polycarbonate polyols, polyacryl polyols, polyolefin polyols, castor oil polyols, polyhydric alcohols, and the like; and copolymers thereof. These polyols can be appropriately determined according to the use in which the foamed cured product is used, and may be used alone or in combination of two or more.
前記ポリエーテルポリオールとしては、例えば、多価アルコールとアルキレンオキサイドとの重合物を用いることができる。 As the polyether polyol, for example, a polymer of polyhydric alcohol and alkylene oxide can be used.
前記多価アルコールとしては、例えば、エチレングリコール、1,2−プロピレングリコール、1,3−プロピレングリコール、1,3−ブチレングリコール、1,4−ブチレングリコール、1,5−ペンタンジオール、2,2−ジメチル−1,3−プロパンジオール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、1,8−オクタンジオール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、シクロヘキサン−1,4−ジオール、シクロヘキサン−1,4−ジメタノール等のグリコール;ポリエステルポリオールなどを用いることができる。これらの化合物は単独で用いても2種以上を併用してもよい。 Examples of the polyhydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 2,2 -Dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane Glycols such as -1,4-diol and cyclohexane-1,4-dimethanol; polyester polyols and the like can be used. These compounds may be used alone or in combination of two or more.
前記アルキレンオキサイドとしては、例えば、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、スチレンオキサイド等を用いることができる。これらの化合物は単独で用いても2種以上を併用してもよい。 Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. These compounds may be used alone or in combination of two or more.
前記ポリエステルポリオールとしては、例えば、多価アルコールと多塩基酸との重合物;前記ポリエーテルポリオールとラクトン化合物との重合物等を用いることができる。 Examples of the polyester polyol include a polymer of a polyhydric alcohol and a polybasic acid; a polymer of the polyether polyol and a lactone compound.
前記多価アルコールとしては、例えば、エチレングリコール、1,2−プロピレングリコール、1,3−プロピレングリコール、1,3−ブチレングリコール、1,4−ブチレングリコール、2,2−ジメチル−1,3−プロパンジオール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、1,8−オクタンジオール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、シクロヘキサン−1,4−ジオール、シクロヘキサン−1,4−ジメタノール、ビスフェノールAのエチレンオキサイド又はプロピレンオキサイド付加物等を用いることができる。これらの多価アルコールは単独で用いても2種以上を併用してもよい。 Examples of the polyhydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,2-dimethyl-1,3- Propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, Cyclohexane-1,4-dimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, and the like can be used. These polyhydric alcohols may be used alone or in combination of two or more.
前記多塩基酸としては、例えば、コハク酸、マレイン酸、アジピン酸、グルタル酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸、フタル酸、イソフタル酸、テレフタル酸、ヘキサヒドロイソフタル酸等を用いることができる。これらの多塩基酸は単独で用いても2種以上を併用してもよい。 Examples of the polybasic acid include succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydroisophthalic acid Etc. can be used. These polybasic acids may be used alone or in combination of two or more.
前記ラクトン化合物としては、例えば、γ−ブチロラクトン、ε−カプロラクトンを開環付加させた重合物も用いることができる。 As the lactone compound, for example, a polymer obtained by ring-opening addition of γ-butyrolactone or ε-caprolactone can also be used.
前記ポリカーボネートポリオールとしては、例えば、炭酸エステル及び/又はホスゲンと、水酸基を2個以上有する化合物とを反応させて得られるものを用いることができる。 As said polycarbonate polyol, what is obtained by making carbonate ester and / or phosgene react with the compound which has 2 or more of hydroxyl groups can be used, for example.
前記炭酸エステルとしては、例えば、ジメチルカーボネート、ジエチルカーボネート、ジフェニルカーボネート、エチレンカーボネート、プロピレンカーボネート等を用いることができる。これらの化合物は単独で用いても2種以上を併用してもよい。 As said carbonate ester, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. can be used, for example. These compounds may be used alone or in combination of two or more.
前記水酸基を2個以上有する化合物としては、例えば、エチレングリコール、プロピレングリコール、1,3−プロパンジオール、1,4−ブタンジオール、1,3−ブタンジオール、1,2−ブタンジオール、2−メチル−1,3−プロパンジオール、1,5−ペンタンジオール、ネオペンチルグリコール、1,6−ヘキサンジオール、1,5−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、1,7−ヘプタンジオール、1,8−オクタンジオール、1,9−ノナンジオール、1,8−ノナンジオール、2−エチル−2−ブチル−1,3−プロパンジオール、1,10−デカンジオール、1,12−ドデカンジオール、1,4−シクロヘキサンジメタノール、1,3−シクロヘキサンジメタノール、トリメチロールプロパン、トリメチロールエタン、グリセリン等を用いることができる。これらの化合物は単独で用いても2種以上を併用してもよい。 Examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, and 2-methyl. -1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 1,7-heptanediol 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,10-decanediol, 1,12-dodecanediol 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane Trimethylol ethane, it can be used glycerin. These compounds may be used alone or in combination of two or more.
前記ポリオール(b3)としては、前記した中でも、前記ホットメルトウレタンプレポリマー(A)と反応して良好な風合いを有する発泡硬化物や合成皮革が得られる点から、ポリエーテルポリオールを用いることが好ましく、ポリオキシプロピレンポリオールを用いることが好ましく、ポリオキシプロピレントリオール及び/又はグリセリンとプロピレンオキサイドとの重合物を用いることがより好ましい。 Among the above-described polyols (b3), polyether polyols are preferably used from the viewpoint of reacting with the hot melt urethane prepolymer (A) to obtain a foamed cured product or synthetic leather having a good texture. Polyoxypropylene polyol is preferably used, and a polymer of polyoxypropylene triol and / or glycerin and propylene oxide is more preferably used.
前記ポリオール(b3)の数平均分子量としては、前記ホットメルトウレタンプレポリマー(A)に混合しやすい点から、500〜10,000の範囲であることが好ましく、700〜5,000の範囲であることがより好ましい。なお、前記ポリオール(b3)の数平均分子量は、ゲル・パーミエーション・クロマトグラフィー(GPC)法により、下記の条件で測定した値を示す。 The number average molecular weight of the polyol (b3) is preferably in the range of 500 to 10,000, more preferably in the range of 700 to 5,000, from the viewpoint of easy mixing with the hot melt urethane prepolymer (A). It is more preferable. In addition, the number average molecular weight of the said polyol (b3) shows the value measured on condition of the following by gel permeation chromatography (GPC) method.
測定装置:高速GPC装置(東ソー株式会社製「HLC−8220GPC」)
カラム:東ソー株式会社製の下記のカラムを直列に接続して使用した。
「TSKgel G5000」(7.8mmI.D.×30cm)×1本
「TSKgel G4000」(7.8mmI.D.×30cm)×1本
「TSKgel G3000」(7.8mmI.D.×30cm)×1本
「TSKgel G2000」(7.8mmI.D.×30cm)×1本
検出器:RI(示差屈折計)
カラム温度:40℃
溶離液:テトラヒドロフラン(THF)
流速:1.0mL/分
注入量:100μL(試料濃度0.4質量%のテトラヒドロフラン溶液)
標準試料:下記の標準ポリスチレンを用いて検量線を作成した。Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
(標準ポリスチレン)
東ソー株式会社製「TSKgel 標準ポリスチレン A−500」
東ソー株式会社製「TSKgel 標準ポリスチレン A−1000」
東ソー株式会社製「TSKgel 標準ポリスチレン A−2500」
東ソー株式会社製「TSKgel 標準ポリスチレン A−5000」
東ソー株式会社製「TSKgel 標準ポリスチレン F−1」
東ソー株式会社製「TSKgel 標準ポリスチレン F−2」
東ソー株式会社製「TSKgel 標準ポリスチレン F−4」
東ソー株式会社製「TSKgel 標準ポリスチレン F−10」
東ソー株式会社製「TSKgel 標準ポリスチレン F−20」
東ソー株式会社製「TSKgel 標準ポリスチレン F−40」
東ソー株式会社製「TSKgel 標準ポリスチレン F−80」
東ソー株式会社製「TSKgel 標準ポリスチレン F−128」
東ソー株式会社製「TSKgel 標準ポリスチレン F−288」
東ソー株式会社製「TSKgel 標準ポリスチレン F−550」(Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
前記ポリオール(b3)の使用量としては、前記ホットメルトウレタンプレポリマー(A)への混合のしやすさの点、及び発泡硬化物の機械的物性の点から、前記発泡剤組成物(B)中30〜90質量%の範囲であることが好ましく、40〜80質量%の範囲であることがより好ましい。 The amount of the polyol (b3) used is the foaming agent composition (B) from the viewpoint of easy mixing with the hot melt urethane prepolymer (A) and the mechanical properties of the foamed cured product. It is preferable that it is the range of 30-90 mass% inside, and it is more preferable that it is the range of 40-80 mass%.
また、前記N,N’−ジニトロソペンタメチレンテトラミン(b1)及び尿素(b2)の合計質量と前記ポリオール(b3)との質量比[(b1)+(b2)/(b3)]としては、ペースト状とならず流動性を確保できるため良好な作業性が得られる点、及び前記ホットメルトウレタンプレポリマー(A)との良好な混合性の点から、10/90〜70/30の範囲であることが好ましく、30/70〜60/40の範囲であることがより好ましい。 In addition, as a mass ratio [(b1) + (b2) / (b3)] of the total mass of the N, N′-dinitrosopentamethylenetetramine (b1) and urea (b2) and the polyol (b3), In the range of 10/90 to 70/30 from the point that good workability can be obtained because the fluidity can be secured without becoming a paste, and from the point of good mixing with the hot melt urethane prepolymer (A). It is preferable that it is in a range of 30/70 to 60/40.
前記発泡剤組成物(B)は、前記(b1)〜(b3)を必須成分として含有するが、必要に応じてその他の添加剤を含有してもよい。 Although the said foaming agent composition (B) contains the said (b1)-(b3) as an essential component, you may contain another additive as needed.
前記その他の添加剤としては、例えば、アゾジカルボンアミド、4,4’−オキシビス(ベンゼンスルホニルヒドラジド)、炭酸水素ナトリウム等の前記(b1)以外の熱分解性発泡剤;ホウ酸(b4)などを用いることができる。これらの添加剤は単独で用いても2種以上を併用してもよい。これらの中でも、前記尿素(b2)の発泡助剤機能を一層高め、より大きな形状の泡を形成でき、一層優れた風合いを有する発泡硬化物や合成皮革が得られる点から、ホウ酸(b4)を用いることが好ましい。 Examples of the other additives include azodicarbonamide, 4,4′-oxybis (benzenesulfonylhydrazide), sodium hydrogen carbonate and other thermally decomposable foaming agents other than the above (b1); boric acid (b4) and the like. Can be used. These additives may be used alone or in combination of two or more. Among these, boric acid (b4) from the point that the foaming auxiliary agent function of the urea (b2) can be further enhanced, foams of a larger shape can be formed, and a foamed cured product and synthetic leather having a better texture can be obtained. Is preferably used.
前記ホウ酸(b4)を用いる場合の使用量としては、前記尿素(b2)100質量部に対して、5〜150質量部の範囲であることが好ましく、10〜120質量部の範囲であることがより好ましい。 When the boric acid (b4) is used, the amount used is preferably in the range of 5 to 150 parts by mass and in the range of 10 to 120 parts by mass with respect to 100 parts by mass of the urea (b2). Is more preferable.
前記発泡剤組成物(B)の使用量としては、発泡硬化物の機械的物性の低下を引き起こすことなく、良好な風合いを有する発泡硬化物や合成皮革が得られ、薄膜でも良好な発泡状態を保持することができる点から、前記ホットメルトウレタンプレポリマー(A)100質量部に対して、1〜30質量部の範囲であることが好ましく、5〜25質量部の範囲であることがより好ましい。 As the amount of the foaming agent composition (B) used, a foamed cured product or synthetic leather having a good texture can be obtained without causing a decrease in the mechanical properties of the foamed cured product. From the point which can be hold | maintained, it is preferable that it is the range of 1-30 mass parts with respect to 100 mass parts of said hot melt urethane prepolymer (A), and it is more preferable that it is the range of 5-25 mass parts. .
前記イソシアネート基を有するホットメルトウレタンプレポリマー(A)は、常温では固体であり、好ましくは80〜120℃の温度で溶融するものである。前記ホットメルトウレタンプレポリマー(A)は、好ましくはコーンプレート粘度計により測定した100℃における溶融粘度が100〜100,000mPa・sの範囲であるものであり、より好ましくは500〜70,000mPa・sの範囲のものである。なお、前記ホットメルトウレタンプレポリマー(A)の溶融粘度は、前記ホットメルトウレタンプレポリマー(A)を100℃で1時間溶融した後、コーンプレート粘度計(M・S・Tエンジニアリング株式会社製デジタルコーンビスメーター「CV−1S RTタイプ」)を使用して測定した値を示す。 The hot melt urethane prepolymer (A) having an isocyanate group is solid at room temperature, and preferably melts at a temperature of 80 to 120 ° C. The hot melt urethane prepolymer (A) preferably has a melt viscosity at 100 ° C. measured by a cone plate viscometer in the range of 100 to 100,000 mPa · s, more preferably 500 to 70,000 mPa · s. It is in the range of s. The melt viscosity of the hot melt urethane prepolymer (A) is determined by melting the hot melt urethane prepolymer (A) at 100 ° C. for 1 hour, and then adding a cone plate viscometer (digitally manufactured by MS Engineering Co., Ltd.). The value measured using a cone bismeter “CV-1S RT type”) is shown.
前記ホットメルトウレタンプレポリマー(A)としては公知のものを用いることができ、例えば、ポリオール(a1)とポリイソシアネート(a2)との反応物を用いることができる。 A well-known thing can be used as said hot-melt-urethane prepolymer (A), For example, the reaction material of polyol (a1) and polyisocyanate (a2) can be used.
前記ポリオール(a1)としては、前記ポリオール(b3)と同様のものを用いることができ、これらのポリオールは使用される用途に応じて適宜決定でき、単独で用いても2種以上を併用してもよい。これらの中でも、本発明の合成皮革が、優れた耐屈曲性、及び耐加水分解性が求められる用途で使用される場合には、ポリオキシテトラメチレングリコールをポリオール(a1)中50質量%以上用いることが好ましく、60〜90質量%の範囲で用いることがより好ましい。また、本発明の合成皮革が、優れた耐久性が求められる用途で使用される場合には、ポリカーボネートポリオールをポリオール(a1)中50質量%以上用いることが好ましく、60〜90質量%の範囲で用いることがより好ましい。 As said polyol (a1), the thing similar to the said polyol (b3) can be used, These polyols can be suitably determined according to the use used, and even if it uses independently, 2 or more types are used together. Also good. Among these, when the synthetic leather of the present invention is used in applications requiring excellent flex resistance and hydrolysis resistance, polyoxytetramethylene glycol is used in an amount of 50% by mass or more in the polyol (a1). It is preferable to use in the range of 60 to 90% by mass. Further, when the synthetic leather of the present invention is used in applications where excellent durability is required, it is preferable to use 50% by mass or more of polycarbonate polyol in the polyol (a1), and in the range of 60 to 90% by mass. More preferably, it is used.
また、前記ポリオール(a1)としてポリオキシテトラメチレングリコールを用いる場合には、凝集力が向上することにより一層優れた耐屈曲性、耐加水分解性、及び耐熱性が得られ、薄膜においても良好な発泡状態を形成できる点から、ポリエステルポリオールを併用することが好ましく、芳香族ポリエステルポリオールを併用することがより好ましい。また、前記ポリオール(a1)としてポリカーボネートポリオールを用いる場合には、凝集力が向上することにより一層優れた柔軟性、耐加水分解性及び耐熱性が得られ、薄膜においても良好な発泡状態を形成できる点から、ポリエステルポリオールを併用することが好ましい。 In addition, when polyoxytetramethylene glycol is used as the polyol (a1), more excellent bending resistance, hydrolysis resistance, and heat resistance can be obtained by improving the cohesive force, and the thin film is also good. From the viewpoint that a foamed state can be formed, it is preferable to use a polyester polyol in combination, and it is more preferable to use an aromatic polyester polyol in combination. Further, when polycarbonate polyol is used as the polyol (a1), more excellent flexibility, hydrolysis resistance and heat resistance can be obtained by improving cohesion, and a good foamed state can be formed even in a thin film. From the viewpoint, it is preferable to use a polyester polyol in combination.
前記ポリオール(a1)の数平均分子量としては、機械的物性の点から、500〜7,000の範囲であることが好ましく、700〜4,000の範囲であることがより好ましい。なお、前記ポリオール(a1)の数平均分子量は、前記ポリオール(b3)の数平均分子量と同様に測定して得られた値を示す。 The number average molecular weight of the polyol (a1) is preferably in the range of 500 to 7,000 and more preferably in the range of 700 to 4,000 from the viewpoint of mechanical properties. In addition, the number average molecular weight of the said polyol (a1) shows the value obtained by measuring similarly to the number average molecular weight of the said polyol (b3).
前記ポリイソシアネート(a2)としては、例えば、ポリメチレンポリフェニルポリイソシアネート、ジフェニルメタンジイソシアネート、ポリメリックジフェニルメタンジイソシアネート、カルボジイミド変性ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、フェニレンジイソシアネート、トリレンジイソシアネート、ナフタレンジイソシアネート等の芳香族ポリイソシアネート;ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート等の脂肪族又は脂環族ポリイソシアネートなどを用いることができる。これらのポリイソシアネートは単独で用いても2種以上を併用してもよい。これらの中でも、良好な反応性及び機械的物性が得られる点から、芳香族ポリイソシアネートを用いることが好ましく、ジフェニルメタンジイソシアネート及び/又はキシリレンジイソシアネートを用いることがより好ましい。 Examples of the polyisocyanate (a2) include aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; Aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, aromatic polyisocyanate is preferably used, and diphenylmethane diisocyanate and / or xylylene diisocyanate is more preferably used from the viewpoint that good reactivity and mechanical properties can be obtained.
前記ホットメルトウレタンプレポリマー(A)の製造方法としては、例えば、前記ポリイソシアネート(a2)の入った反応容器に、前記ポリオール(a1)を滴下した後に加熱し、前記ポリイソシアネート(a2)の有するイソシアネート基が、前記ポリオール(a1)の有する水酸基に対して過剰となる条件で反応させることによって製造することができる。 As a manufacturing method of the said hot melt urethane prepolymer (A), it heats, after dripping the said polyol (a1) in the reaction container containing the said polyisocyanate (a2), for example, and the said polyisocyanate (a2) has It can manufacture by making it react on the conditions which an isocyanate group becomes excess with respect to the hydroxyl group which the said polyol (a1) has.
前記ホットメルトウレタンプレポリマー(A)を製造する際の、前記ポリイソシアネート(a2)が有するイソシアネート基と前記ポリオール(a1)が有する水酸基の当量比([NCO/OH])としては、機械的強度の点から、1.1〜5の範囲であることが好ましく、1.5〜3.5の範囲であることがより好ましい。 When producing the hot melt urethane prepolymer (A), the equivalent ratio ([NCO / OH]) of the isocyanate group of the polyisocyanate (a2) and the hydroxyl group of the polyol (a1) is mechanical strength. From this point, it is preferably in the range of 1.1 to 5, and more preferably in the range of 1.5 to 3.5.
前記ホットメルトウレタンプレポリマー(A)のイソシアネート基含有率(以下、「NCO%」と略記する。)としては、機械的強度の点から、1.1〜5質量%の範囲が好ましく、1.5〜4質量%の範囲がより好ましい。なお、前記前記ホットメルトウレタンプレポリマー(A)のイソシアネート基含有率は、JISK1603−1:2007に準拠し、電位差滴定法により測定した値を示す。 The isocyanate group content (hereinafter abbreviated as “NCO%”) of the hot melt urethane prepolymer (A) is preferably in the range of 1.1 to 5 mass% from the viewpoint of mechanical strength. The range of 5-4 mass% is more preferable. In addition, the isocyanate group content rate of the said hot melt urethane prepolymer (A) shows the value measured by the potentiometric titration method based on JISK1603-1: 2007.
本発明の湿気硬化型ホットメルトウレタン組成物は、前記ホットメルトウレタンプレポリマー(A)及び前記発泡剤組成物(B)を必須成分として含有するものであるが、必要に応じてその他の添加剤を含有してもよい。 The moisture curable hot melt urethane composition of the present invention contains the hot melt urethane prepolymer (A) and the foaming agent composition (B) as essential components, and other additives as necessary. It may contain.
前記その他の添加剤としては、例えば、ウレタン化触媒、シランカップリング剤、チキソ性付与剤、酸化防止剤、可塑剤、充填材、染料、顔料、ワックス等を用いることができる。これらの添加剤は単独で用いても2種以上を併用してもよい。 Examples of the other additives include urethanization catalysts, silane coupling agents, thixotropic agents, antioxidants, plasticizers, fillers, dyes, pigments, and waxes. These additives may be used alone or in combination of two or more.
次に、前記湿気硬化型ホットメルトウレタン組成物の発泡硬化物の製造方法について説明する。 Next, a method for producing a foam cured product of the moisture curable hot melt urethane composition will be described.
本発明である前記湿気硬化型ホットメルトウレタン組成物の発泡硬化物の製造方法は、前記イソシアネート基を有するホットメルトウレタンプレポリマー(A)を加熱溶融した後に、N,N’−ジニトロソペンタメチレンテトラミン(b1)、尿素(b2)、及びポリオール(b3)を含む発泡剤組成物(B)を前記加熱溶融されたホットメルトウレタンプレポリマー(A)に混合し、該混合物を基材に塗布し、次いで、前記ホットメルトウレタンプレポリマー(A)の加熱溶融温度以上の温度で加熱処理をすることにより発泡硬化することを必須要件とする。 In the method for producing a foamed cured product of the moisture-curable hot melt urethane composition according to the present invention, the hot melt urethane prepolymer (A) having an isocyanate group is heated and melted, and then N, N′-dinitrosopentamethylene is used. A foaming agent composition (B) containing tetramine (b1), urea (b2), and polyol (b3) is mixed with the hot-melted hot-melt urethane prepolymer (A), and the mixture is applied to a substrate. Then, it is an essential requirement that foam curing is performed by heat treatment at a temperature equal to or higher than the heat melting temperature of the hot melt urethane prepolymer (A).
前記ホットメルトウレタンプレポリマー(A)の加熱溶融温度としては、例えば、80〜120℃の範囲である。 The heating and melting temperature of the hot melt urethane prepolymer (A) is, for example, in the range of 80 to 120 ° C.
前記発泡剤組成物(B)は、前記(b1)〜(b3)、及び好ましくは前記(b4)を撹拌して混合し、ポリオール(b3)中で前記(b1)、(b2)及び好ましくは(b4)が均一に分散されていることが好ましい。また、前記発泡剤組成物(B)は前記ホットメルトウレタンプレポリマー(A)と混合させる前に、例えば25〜100℃の温度で加温していてもよい。 In the blowing agent composition (B), the (b1) to (b3), and preferably the (b4) are stirred and mixed, and the (b1), (b2) and preferably in the polyol (b3). It is preferable that (b4) is uniformly dispersed. Moreover, the said foaming agent composition (B) may be heated, for example at the temperature of 25-100 degreeC, before making it mix with the said hot melt urethane prepolymer (A).
前記発泡剤組成物(B)を、加熱溶融されたホットメルトウレタンプレポリマー(A)と混合する方法としては、例えば、バッチ式の攪拌機、スタティックミキサー、ローターステーター、2液混合装置等の混合装置等を使用する方法が挙げられる。 Examples of the method of mixing the foaming agent composition (B) with the hot-melt urethane prepolymer (A) that has been heated and melted include, for example, a mixing device such as a batch type stirrer, a static mixer, a rotor stator, and a two-component mixing device. And the like.
なお、前記ホットメルトウレタンプレポリマー(A)と前記発泡剤組成物(B)とを混合した際には、混合時に巻き込まれる泡や、前記ホットメルトウレタンポレポリマー(A)が有するイソシアネート基と一部の尿素(b2)とが反応して炭酸ガスが発生する場合がある。 In addition, when the said hot melt urethane prepolymer (A) and the said foaming agent composition (B) are mixed, with the isocyanate group which the said hot-melt urethane-prepolymer (A) has, and the foam wound up at the time of mixing Part of urea (b2) may react to generate carbon dioxide gas.
前記(A)と(B)との混合物を基材に塗布する方法としては、例えば、アプリケーター、ロールコーター、スプレーコーター、T−ダイコーター、ナイフコーター、コンマコーター等を使用した方法が挙げられる。 Examples of the method for applying the mixture of (A) and (B) to the substrate include a method using an applicator, roll coater, spray coater, T-die coater, knife coater, comma coater, and the like.
なお、前記(A)と(B)との混合物の塗布物は、後述する後加熱により発泡し厚さが増大するため、後述する発泡度等を考慮した上で前記塗布時の厚さを決定することが好ましい。 In addition, since the coating of the mixture of (A) and (B) is foamed by post-heating described later and increases in thickness, the thickness at the time of coating is determined in consideration of the degree of foaming described later. It is preferable to do.
前記基材としては、例えば、ポリエステル繊維、ナイロン繊維、アクリル繊維、ポリウレタン繊維、アセテート繊維、レーヨン繊維、ポリ乳酸繊維、綿、麻、絹、羊毛、それらの混紡繊維等による不織布、織布、編み物;離型紙などを用いることができる。更に、前記基材としては、板、MDF(ミディアム デンシティ ファイバーボード)、パーチクルボード等の木質基材;アルミ、鉄等の金属基材;ポリカーボネート基材、シクロオレフィン樹脂基材、アクリル樹脂基材、シリコン樹脂基材、エポキシ樹脂基材、フッ素樹脂基材、ポリスチレン樹脂基材、ポリエステル樹脂基材、ポリスルホン樹脂基材、ポリアリレート樹脂基材、ポリ塩化ビニル樹脂基材、ポリ塩化ビニリデン基材、非結晶性ポリオレフィン樹脂基材、ポリイミド樹脂基材、脂環式ポリイミド樹脂基材、セルロース樹脂基材、TAC(トリアセチルセルロース)基材、COP(シクロオレフィンポリマー)基材、PC(ポリカーボネート)基材、PBT(ポリブチレンテレフタラート)基材、変性PPE(ポリフェニレンエーテル)基材、PEN(ポリエチレンナフタレート)基材、PET(ポリエチレンテレフタラート)基材、ポリ乳酸ポリマー基材等のプラスチック基材;ガラス板などを用いることができる。また、前記基材は、溝部、R部、逆R部等の複雑な形状の部位を有していてもよい。 Examples of the base material include polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, polylactic acid fibers, cotton, hemp, silk, wool, non-woven fabrics, woven fabrics, and knitted fabrics thereof. Release paper or the like can be used. Furthermore, as the base material, wood base materials such as plates, MDF (medium density fiber board), particle boards; metal base materials such as aluminum and iron; polycarbonate base materials, cycloolefin resin base materials, acrylic resin base materials, silicon Resin substrate, epoxy resin substrate, fluororesin substrate, polystyrene resin substrate, polyester resin substrate, polysulfone resin substrate, polyarylate resin substrate, polyvinyl chloride resin substrate, polyvinylidene chloride substrate, amorphous Polyolefin resin substrate, polyimide resin substrate, alicyclic polyimide resin substrate, cellulose resin substrate, TAC (triacetylcellulose) substrate, COP (cycloolefin polymer) substrate, PC (polycarbonate) substrate, PBT (Polybutylene terephthalate) base material, modified PPE (polyphenylene ether) Ter) base material, PEN (polyethylene naphthalate) base material, PET (polyethylene terephthalate) base material, plastic base material such as polylactic acid polymer base material; glass plate and the like can be used. Further, the base material may have a complicated shape such as a groove, an R portion, and an inverted R portion.
前記基材上に前記(A)と(B)との混合物を塗布した後は、該塗布面上に前記基材を更に貼り合わせてもよい。 After the mixture of the (A) and (B) is applied on the base material, the base material may be further bonded onto the application surface.
次に、前記基材及び前記(A)と(B)との混合物を有する積層体を、前記ホットメルトウレタンプレポリマー(A)の加熱溶融温度以上の温度で加熱処理することで、前記発泡剤組成物(B)(特に、前記(b1))の発泡・硬化を促進する。この際の前記加熱処理としては、例えば、100〜150℃の範囲であり、基材への悪影響や熱履歴による発泡硬化物の物性低下を抑制しやすい点から、110〜140℃の範囲であることがより好ましい。前記加熱処理の時間としては、例えば、1〜10分間であることが好ましい。 Next, the foaming agent is obtained by heat-treating the laminate having the base material and the mixture of (A) and (B) at a temperature equal to or higher than the heat-melting temperature of the hot-melt urethane prepolymer (A). The foaming / curing of the composition (B) (particularly (b1) above) is promoted. The heat treatment at this time is, for example, in the range of 100 to 150 ° C., and in the range of 110 to 140 ° C. from the viewpoint of easily suppressing adverse effects on the base material and physical properties of the foamed cured product due to thermal history. It is more preferable. The heat treatment time is preferably 1 to 10 minutes, for example.
前記加熱処理した後は、必要に応じて、例えば、20〜80℃の温度で、1〜7日間アフタキュアを行ってもよい。 After the heat treatment, after-curing may be performed at a temperature of 20 to 80 ° C. for 1 to 7 days as necessary.
以上の方法により得られた湿気硬化型ホットメルト組成物の発泡硬化物層の厚さとしては、例えば、10〜500μmの範囲であり、この範囲内で良好な発泡状態を形成することができる。前記厚さは、前記発泡硬化物が使用される用途に応じて適宜決定することができる。また、本発明においては、薄膜においても良好な発泡状態を保持することができ、その厚さとしては、例えば100μm未満、好ましくは20〜90μmの範囲、より好ましくは30〜80μmの範囲であり、特に好ましくは40〜70μmの範囲である。 The thickness of the foam cured product layer of the moisture curable hot melt composition obtained by the above method is, for example, in the range of 10 to 500 μm, and a good foamed state can be formed within this range. The said thickness can be suitably determined according to the use for which the said foaming hardened | cured material is used. In the present invention, a good foamed state can be maintained even in a thin film, and the thickness thereof is, for example, less than 100 μm, preferably in the range of 20 to 90 μm, more preferably in the range of 30 to 80 μm. Especially preferably, it is the range of 40-70 micrometers.
前記発泡硬化物中に残存する泡としては、前記(b1)の後加熱による発泡が主であるが、前記発泡硬化物の発泡度としては、1.2以上であることが好ましく、1.5〜3の範囲であることがより好ましく、1.7〜2.8の範囲であることが更に好ましい。なお、前記発泡硬化物の発泡度は、前記(A)と(B)の混合物の発泡前の体積(V1)と、発泡後の体積(V2)との比(V2/V1)から算出した値を示す。The foam remaining in the foamed cured product is mainly foamed by post-heating of (b1), and the foaming degree of the foamed cured product is preferably 1.2 or more. Is more preferably in the range of ˜3, and still more preferably in the range of 1.7 to 2.8. Incidentally, the foaming degree of the foamed cured product, the (A) and before foaming volume of the mixture of (B) (V 1) and, the ratio of the volume after foaming (V 2) (V 2 / V 1) The value calculated from
以上、本発明の湿気硬化型ホットメルトウレタン組成物は、特定の熱分解性発泡剤を用いることにより、良好な風合いを有する発泡硬化物が得られ、薄膜でも良好な発泡状態を保持することができ、発泡後も発泡硬化物の機械的物性の低下を引き起こさないものである。また、水の影響を受けることなく発泡させることができ、湿気硬化型ホットメルトウレタン組成物が溶融状態から一度冷却固化した場合や湿気硬化途中でも、再度加熱処理することで熱分解性発泡剤による発泡を促進することができる。 As described above, the moisture curable hot melt urethane composition of the present invention can obtain a foamed cured product having a good texture by using a specific thermally decomposable foaming agent, and can maintain a good foamed state even in a thin film. The foamed cured product does not cause a decrease in mechanical properties even after foaming. In addition, it can be foamed without being affected by water, and when the moisture-curable hot-melt urethane composition is once cooled and solidified from the melted state or in the course of moisture curing, it can be reheated to produce a heat-decomposable foaming agent. Foaming can be promoted.
次に、本発明の合成皮革について説明する。 Next, the synthetic leather of the present invention will be described.
本発明の合成皮革は、基布(i)、中間層(ii)、及び表皮層(iii)を有し、前記中間層(ii)が、前記湿気硬化型ホットメルトウレタン組成物の発泡硬化物であるものである。 The synthetic leather of the present invention has a base fabric (i), an intermediate layer (ii), and a skin layer (iii), and the intermediate layer (ii) is a foam cured product of the moisture-curable hot-melt urethane composition. It is what is.
前記基布(i)としては、例えば、ポリエステル繊維、ポリエチレン繊維、ナイロン繊維、アクリル繊維、ポリウレタン繊維、アセテート繊維、レーヨン繊維、ポリ乳酸繊維、綿、麻、絹、羊毛、グラスファイバー、炭素繊維、それらの混紡繊維等による不織布、織布、編み物などを用いることができる。 Examples of the base fabric (i) include polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, glass fiber, carbon fiber, Nonwoven fabrics, woven fabrics, knitted fabrics and the like made of these blended fibers can be used.
前記表皮層(iii)としては、公知の材料により公知の方法で形成することができ、例えば、溶剤系ウレタン樹脂、水系ウレタン樹脂、シリコーン樹脂、ポリプロピレン樹脂、ポリエステル樹脂等を用いることができる。前記表皮層(iii)としては、柔軟な風合い、及び耐屈曲性、耐加水分解性を重視する場合は、ポリエーテル系ウレタン樹脂を用いることが好ましく、その中でも特に低温屈曲性を重視する場合は、ポリテトラメチレングリコールを原料とするウレタン樹脂を用いる方がより好ましい。また、柔軟な風合い、耐熱性、及び耐加水分解性を重視する場合には、ポリカーボネートポリオールを原料とするウレタン樹脂を用いることが好ましい。また、環境対応でのDMF低減化のためには、水系ウレタン樹脂を用いる方が好ましい。 As said skin layer (iii), it can form by a well-known method with a well-known material, For example, a solvent-type urethane resin, a water-system urethane resin, a silicone resin, a polypropylene resin, a polyester resin etc. can be used. As the skin layer (iii), it is preferable to use a polyether-based urethane resin when the soft texture, the bending resistance, and the hydrolysis resistance are important, and particularly when the low temperature flexibility is important. It is more preferable to use a urethane resin made from polytetramethylene glycol. Moreover, when importance is attached to a soft texture, heat resistance, and hydrolysis resistance, it is preferable to use a urethane resin made of polycarbonate polyol. In addition, it is preferable to use a water-based urethane resin in order to reduce the DMF for the environment.
前記表皮層(iii)上には、必要に応じて、耐傷性向上等を目的にトップコート層(iv)を設けてもよい。前記トップコート層(iv)としては、公知の材料により公知の方法で形成することができ、前記表皮層(iii)の形成に用いることができる材料と同様のものを用いることができる。 On the skin layer (iii), a top coat layer (iv) may be provided for the purpose of improving scratch resistance, if necessary. The top coat layer (iv) can be formed by a known method using a known material, and the same materials as those that can be used for forming the skin layer (iii) can be used.
次に、本発明の合成皮革の製造方法について説明する。 Next, the manufacturing method of the synthetic leather of this invention is demonstrated.
本発明の合成皮革を製造する方法としては、例えば、
(イ)前記ホットメルトウレタンプレポリマー(A)を加熱溶融した後に、N,N’−ジニトロソペンタメチレンテトラミン(b1)、尿素(b2)、及びポリオール(b3)を含む発泡剤組成物(B)を混合して湿気硬化型ホットメルトウレタン組成物を得、前記湿気硬化型ホットメルト組成物を、離型紙上に形成し記表皮層(iii)上に塗布し、次いで、前記ホットメルトウレタンプレポリマー(A)の加熱溶融温度以上の温度で加熱処理をすることにより中間層(ii)を形成し、次いで前記中間層(ii)上に基布(i)を貼り合せることで合成皮革を製造する方法、As a method for producing the synthetic leather of the present invention, for example,
(A) After the hot melt urethane prepolymer (A) is heated and melted, a foaming agent composition (B) containing N, N′-dinitrosopentamethylenetetramine (b1), urea (b2), and polyol (b3) ) To obtain a moisture curable hot melt urethane composition. The moisture curable hot melt composition is formed on a release paper and coated on the outer skin layer (iii). A synthetic leather is manufactured by forming an intermediate layer (ii) by heating at a temperature equal to or higher than the heat melting temperature of the polymer (A), and then bonding the base fabric (i) on the intermediate layer (ii). how to,
(ロ)前記ホットメルトウレタンプレポリマー(A)を加熱溶融した後に、N,N’−ジニトロソペンタメチレンテトラミン(b1)、尿素(b2)、及びポリオール(b3)を含む発泡剤組成物(B)を混合して湿気硬化型ホットメルトウレタン組成物を得、前記湿気硬化型ホットメルト組成物を、離型紙上に形成した表皮層(iii)上に塗布し、次いで、前記湿気硬化型ホットメルト組成物の塗布層上に、基布(i)を貼り合せてから、前記ホットメルトウレタンプレポリマー(A)の加熱溶融温度以上の温度で加熱処理をすることにより中間層(ii)を形成して合成皮革を製造する方法、 (B) After the hot-melt urethane prepolymer (A) is heated and melted, a blowing agent composition (B) containing N, N′-dinitrosopentamethylenetetramine (b1), urea (b2), and polyol (b3) ) To obtain a moisture curable hot melt urethane composition, the moisture curable hot melt composition is applied onto a skin layer (iii) formed on a release paper, and then the moisture curable hot melt An intermediate layer (ii) is formed by laminating the base fabric (i) on the coating layer of the composition and then heat-treating it at a temperature equal to or higher than the heating and melting temperature of the hot melt urethane prepolymer (A). To produce synthetic leather,
(ハ)前記ホットメルトウレタンプレポリマー(A)を加熱溶融した後に、N,N’−ジニトロソペンタメチレンテトラミン(b1)、尿素(b2)、及びポリオール(b3)を含む発泡剤組成物(B)を混合して湿気硬化型ホットメルトウレタン組成物を得、前記湿気硬化型ホットメルト組成物を、基布(i)上に塗布し、次いで、前記ホットメルトウレタンプレポリマー(A)の加熱溶融温度以上の温度で加熱処理をすることにより中間層(ii)を形成し、次いで前記中間層(ii)に、離型紙上に形成した表皮層(iii)面を貼り合せることで合成皮革を製造する方法、 (C) A foaming agent composition (B) containing N, N′-dinitrosopentamethylenetetramine (b1), urea (b2), and polyol (b3) after the hot melt urethane prepolymer (A) is melted by heating. ) To obtain a moisture curable hot melt urethane composition, apply the moisture curable hot melt composition onto the base fabric (i), and then heat and melt the hot melt urethane prepolymer (A) An intermediate layer (ii) is formed by heat treatment at a temperature higher than the temperature, and then synthetic leather is manufactured by laminating the surface layer (iii) surface formed on the release paper to the intermediate layer (ii). how to,
(ニ)前記ホットメルトウレタンプレポリマー(A)を加熱溶融した後に、N,N’−ジニトロソペンタメチレンテトラミン(b1)、尿素(b2)、及びポリオール(b3)を含む発泡剤組成物(B)を混合して湿気硬化型ホットメルトウレタン組成物を得、前記湿気硬化型ホットメルト組成物を、基布(i)上に塗布し、次いで、前記湿気硬化型ホットメルト組成物の塗布層上に、離型紙上に形成した表皮層(iii)面を貼り合せてから、前記ホットメルトウレタンプレポリマー(A)の加熱溶融温度以上の温度で加熱処理をすることにより中間層(ii)を形成して合成皮革を製造する方法等が挙げられる。 (D) A foaming agent composition (B) containing N, N′-dinitrosopentamethylenetetramine (b1), urea (b2), and polyol (b3) after the hot melt urethane prepolymer (A) is melted by heating. ) To obtain a moisture curable hot melt urethane composition, the moisture curable hot melt composition is applied onto the base fabric (i), and then applied to the moisture curable hot melt composition. The intermediate layer (ii) is formed by bonding the surface of the skin layer (iii) formed on the release paper to the hot melt urethane prepolymer (A) at a temperature equal to or higher than the heating and melting temperature. And a method for producing synthetic leather.
これらの中でも、中間層(ii)の発泡(製造)安定性、及び、中間層(ii)の厚さを一定にしやすい点から、前記(イ)による製造方法を使用することが好ましい。 Among these, it is preferable to use the manufacturing method according to the above (a) from the viewpoint that the foaming (manufacturing) stability of the intermediate layer (ii) and the thickness of the intermediate layer (ii) are easily made constant.
前記ホットメルトウレタンプレポリマー(A)の加熱溶融温度としては、例えば、80〜120℃の範囲である。 The heating and melting temperature of the hot melt urethane prepolymer (A) is, for example, in the range of 80 to 120 ° C.
前記発泡剤組成物(B)は、前記(b1)〜(b3)、及び好ましくは前記(b4)を撹拌して混合し、ポリオール(b3)中で前記(b1)、(b2)及び好ましくは(b4)が、バッチ式の攪拌機、スタティックミキサー、ローターステーター、2本ロール、3本ロール、ビーズミル等を使用して均一に分散されていることが好ましい。また、前記発泡剤組成物(B)は前記ホットメルトウレタンプレポリマー(A)と混合させる前に、例えば25〜100℃の温度で加温していてもよい。 In the blowing agent composition (B), the (b1) to (b3), and preferably the (b4) are stirred and mixed, and the (b1), (b2) and preferably in the polyol (b3). (B4) is preferably uniformly dispersed using a batch-type stirrer, static mixer, rotor stator, two rolls, three rolls, bead mill, or the like. Moreover, the said foaming agent composition (B) may be heated, for example at the temperature of 25-100 degreeC, before making it mix with the said hot melt urethane prepolymer (A).
前記発泡剤組成物(B)を、加熱溶融されたホットメルトウレタンプレポリマー(A)と混合する方法としては、例えば、バッチ式の攪拌機、スタティックミキサー、ローターステーター、2液混合装置等の混合装置等を使用する方法が挙げられる。 Examples of the method of mixing the foaming agent composition (B) with the hot-melt urethane prepolymer (A) that has been heated and melted include, for example, a mixing device such as a batch type stirrer, a static mixer, a rotor stator, and a two-component mixing device. And the like.
なお、前記ホットメルトウレタンプレポリマー(A)と前記発泡剤組成物(B)とを混合した際には、混合時に巻き込まれる泡や、前記ホットメルトウレタンポレポリマー(A)が有するイソシアネート基と一部の尿素(b2)とが反応して炭酸ガスが発生する場合がある。 In addition, when the said hot melt urethane prepolymer (A) and the said foaming agent composition (B) are mixed, with the isocyanate group which the said hot-melt urethane-prepolymer (A) has, and the foam wound up at the time of mixing Part of urea (b2) may react to generate carbon dioxide gas.
前記湿気硬化型ホットメルトウレタン組成物を、離型紙に形成した表皮層(iii)上に塗布する方法としては、例えば、アプリケーター、ロールコーター、スプレーコーター、T−ダイコーター、ナイフコーター、コンマコーター等を使用した方法が挙げられる。 Examples of the method for applying the moisture-curable hot melt urethane composition onto the skin layer (iii) formed on the release paper include an applicator, a roll coater, a spray coater, a T-die coater, a knife coater, and a comma coater. The method using is mentioned.
なお、前記湿気硬化型ホットメルトウレタン組成物の塗布物は、後述する後加熱により発泡し厚さが増大するため、後述する発泡度等を考慮した上で前記塗布時の厚さを決定することが好ましい。 In addition, since the coated product of the moisture-curable hot melt urethane composition is foamed by post-heating described later and increases in thickness, the thickness at the time of coating is determined in consideration of the foaming degree described later. Is preferred.
次に、前記ホットメルトウレタンプレポリマー(A)の加熱溶融温度以上の温度で加熱処理することで、前記発泡剤組成物(B)(特に、前記(b1))の発泡・硬化を促進して、中間層(ii)を製造する。この際の前記加熱処理としては、例えば、100〜150℃の範囲であり、基材への悪影響や熱履歴による合成皮革の物性低下を抑制しやすい点から、110〜140℃の範囲であることがより好ましい。前記加熱処理の時間としては、例えば、1〜10分間であることが好ましい。 Next, the foaming / curing of the foaming agent composition (B) (particularly the (b1)) is promoted by heat treatment at a temperature equal to or higher than the heat-melting temperature of the hot-melt urethane prepolymer (A). The intermediate layer (ii) is produced. In this case, the heat treatment is, for example, in the range of 100 to 150 ° C., and in the range of 110 to 140 ° C. from the viewpoint of easily suppressing adverse effects on the base material and deterioration of physical properties of the synthetic leather due to thermal history. Is more preferable. The heat treatment time is preferably 1 to 10 minutes, for example.
前記中間層(ii)を形成した後には、前記中間層(ii)上に基布(i)を貼り合せることで合成皮革を得ることできるが、前記基布(i)を貼り合せる前、及び/又は後においては、中間層(ii)の熟成を目的に、例えば、20〜80℃の温度で、1〜7日間アフタキュアを行ってもよい。 After forming the intermediate layer (ii), synthetic leather can be obtained by laminating the base fabric (i) on the intermediate layer (ii), but before laminating the base fabric (i), and In the following, after-curing may be performed, for example, at a temperature of 20 to 80 ° C. for 1 to 7 days for the purpose of aging the intermediate layer (ii).
以上の方法により得られた合成皮革の中間層(ii)の厚さとしては、例えば、10〜500μmの範囲であり、この範囲内で良好な発泡状態を形成することができる。前記厚さは、本発明の合成皮革が使用される用途に応じて適宜決定することができる。また、本発明においては、薄膜においても良好な発泡状態を保持することができ、その厚さとしては、例えば100μm未満、好ましくは20〜90μmの範囲、より好ましくは30〜80μmの範囲であり、特に好ましくは50〜70μmの範囲である。 The thickness of the intermediate layer (ii) of the synthetic leather obtained by the above method is, for example, in the range of 10 to 500 μm, and a good foamed state can be formed within this range. The said thickness can be suitably determined according to the use for which the synthetic leather of this invention is used. In the present invention, a good foamed state can be maintained even in a thin film, and the thickness thereof is, for example, less than 100 μm, preferably in the range of 20 to 90 μm, more preferably in the range of 30 to 80 μm. Especially preferably, it is the range of 50-70 micrometers.
前記中間層(ii)中に残存する泡としては、前記(b1)の後加熱による発泡が主であるが、前記中間層(ii)の発泡度としては、1.2以上であることが好ましく、1.5〜3の範囲であることがより好ましく、1.7〜2.8の範囲であることが更に好ましい。なお、前記中間層(ii)の発泡度は、前記湿気硬化型ホットメルトウレタン組成物の発泡前の体積(V1)と、発泡後の体積(V2)との比(V2/V1)から算出した値を示す。The foam remaining in the intermediate layer (ii) is mainly foamed by post-heating of (b1), but the degree of foaming of the intermediate layer (ii) is preferably 1.2 or more. The range of 1.5 to 3 is more preferable, and the range of 1.7 to 2.8 is more preferable. Incidentally, degree of foaming of the intermediate layer (ii), the moisture-curable and before foaming of the volume of hot melt urethane composition (V 1), the ratio of the volume after foaming (V 2) (V 2 / V 1 The value calculated from
以下、実施例を用いて、本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
[合成例1]ホットメルトウレタンプレポリマー(A−1)の合成
温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた反応容器に、ポリオキシテトラメチレングリコール(数平均分子量;2,000)を70質量部、ポリエステルポリオール(1)(1,6−ヘキサンジオールとアジピン酸との反応物、数平均分子量;2,000)を30質量部、を仕込み、減圧条件下で水分含有率が0.05質量%以下となるまで脱水した。
次いで、4,4’−ジフェニルメタンジイソシアネートを25質量部を加え、100℃まで昇温して、イソシアネート基含有率が一定となるまで約3時間反応させて、NCO%;3.3のイソシアネート基を有するホットメルトウレタンプレポリマー(A−1)を得た。[Synthesis Example 1] Synthesis of hot-melt urethane prepolymer (A-1) In a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, polyoxytetramethylene glycol (number average molecular weight; 70 parts by mass of 2,000) and 30 parts by mass of polyester polyol (1) (reaction product of 1,6-hexanediol and adipic acid, number-average molecular weight; 2,000) were charged under reduced pressure conditions. It dehydrated until the content rate became 0.05 mass% or less.
Next, 25 parts by mass of 4,4′-diphenylmethane diisocyanate was added, the temperature was raised to 100 ° C., and the mixture was reacted for about 3 hours until the isocyanate group content became constant. A hot melt urethane prepolymer (A-1) was obtained.
[合成例2]ホットメルトウレタンプレポリマー(A−2)の合成
温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた反応容器に、ポリオキシテトラメチレングリコール(数平均分子量;2,000)を70質量部、ポリエステルポリオール(2)(ビスフェノールAのプロピレンオキシアド6モル付加物とセバシン酸との反応物、数平均分子量;2,000)を30質量部、を仕込み、減圧条件下で水分含有率が0.05質量%以下となるまで脱水した。
次いで、4,4’−ジフェニルメタンジイソシアネートを25質量部を加え、100℃まで昇温して、イソシアネート基含有率が一定となるまで約3時間反応させて、NCO%;3.3のイソシアネート基を有するホットメルトウレタンプレポリマー(A−2)を得た。[Synthesis Example 2] Synthesis of hot melt urethane prepolymer (A-2) In a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, polyoxytetramethylene glycol (number average molecular weight; 70 parts by mass of 2,000), 30 parts by mass of polyester polyol (2) (reaction product of propylene oxyad 6 mol adduct of bisphenol A and sebacic acid, number average molecular weight; 2,000), Dehydration was performed until the water content was 0.05% by mass or less under the conditions.
Next, 25 parts by mass of 4,4′-diphenylmethane diisocyanate was added, the temperature was raised to 100 ° C., and the mixture was reacted for about 3 hours until the isocyanate group content became constant. A hot melt urethane prepolymer (A-2) was obtained.
[合成例3]ホットメルトウレタンプレポリマー(A−3)の合成
温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた反応容器に、ポリカーボネートポリオール(日本ポリウレタン工業株式会社製「ニッポラン980R」、数平均分子量;2,600)を70質量部、ポリエステルポリオール(1)(1,6−ヘキサンジオールとアジピン酸との反応物、数平均分子量;2,000)を30質量部、を仕込み、減圧条件下で水分含有率が0.05質量%以下となるまで脱水した。
次いで、4,4’−ジフェニルメタンジイソシアネートを25質量部を加え、100℃まで昇温して、イソシアネート基含有率が一定となるまで約3時間反応させて、NCO%;3.2のイソシアネート基を有するホットメルトウレタンプレポリマー(A−3)を得た。[Synthesis Example 3] Synthesis of Hot Melt Urethane Prepolymer (A-3) Polycarbonate polyol (manufactured by Nippon Polyurethane Industry Co., Ltd. "" in a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. Nipponran 980R ", number average molecular weight; 2,600) 70 parts by mass, polyester polyol (1) (reaction product of 1,6-hexanediol and adipic acid, number average molecular weight; 2,000) 30 parts by mass, Was dehydrated under reduced pressure until the water content was 0.05% by mass or less.
Next, 25 parts by mass of 4,4′-diphenylmethane diisocyanate was added, the temperature was raised to 100 ° C., and the reaction was allowed to proceed for about 3 hours until the isocyanate group content became constant. A hot melt urethane prepolymer (A-3) was obtained.
[合成例4]ホットメルトウレタンプレポリマー(A−4)の合成
温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた反応容器に、ポリカーボネートポリオール(日本ポリウレタン工業株式会社製「ニッポラン980R」、数平均分子量;2,600)を70質量部、ポリエステルポリオール(2)(ビスフェノールAのプロピレンオキシアド6モル付加物とセバシン酸との反応物、数平均分子量;2,000)を30質量部、を仕込み、減圧条件下で水分含有率が0.05質量%以下となるまで脱水した。
次いで、4,4’−ジフェニルメタンジイソシアネートを25質量部を加え、100℃まで昇温して、イソシアネート基含有率が一定となるまで約3時間反応させて、NCO%;3.2のイソシアネート基を有するホットメルトウレタンプレポリマー(A−4)を得た。[Synthesis Example 4] Synthesis of Hot Melt Urethane Prepolymer (A-4) Polycarbonate polyol (manufactured by Nippon Polyurethane Industry Co., Ltd. "" in a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. NIPPOLAN 980R ", 70 parts by mass of number average molecular weight; 2,600), polyester polyol (2) (reaction product of bisphenol A propylene oxyad 6 mol adduct and sebacic acid, number average molecular weight: 2,000) 30 parts by mass were charged and dehydrated under reduced pressure until the water content was 0.05% by mass or less.
Next, 25 parts by mass of 4,4′-diphenylmethane diisocyanate was added, the temperature was raised to 100 ° C., and the reaction was allowed to proceed for about 3 hours until the isocyanate group content became constant. A hot melt urethane prepolymer (A-4) was obtained.
[合成例5]ホットメルトウレタンプレポリマー(A−5)の合成
温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた反応容器に、ポリオキシテトラメチレングリコール(数平均分子量;2,000)を70質量部、ポリエステルポリオール(1)(1,6−ヘキサンジオールとアジピン酸との反応物、数平均分子量;2,000)を30質量部、を仕込み、減圧条件下で水分含有率が0.05質量%以下となるまで脱水した。
次いで、キシリレンジイソシアネートを18質量部を加え、100℃まで昇温して、イソシアネート基含有率が一定となるまで約3時間反応させて、NCO%;3.2のイソシアネート基を有するホットメルトウレタンプレポリマー(A−5)を得た。Synthesis Example 5 Synthesis of Hot Melt Urethane Prepolymer (A-5) In a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, polyoxytetramethylene glycol (number average molecular weight; 70 parts by mass of 2,000) and 30 parts by mass of polyester polyol (1) (reaction product of 1,6-hexanediol and adipic acid, number-average molecular weight; 2,000) were charged under reduced pressure conditions. It dehydrated until the content rate became 0.05 mass% or less.
Next, 18 parts by mass of xylylene diisocyanate was added, the temperature was raised to 100 ° C., and the reaction was allowed to proceed for about 3 hours until the isocyanate group content became constant, whereby a hot melt urethane having an isocyanate group of NCO%; 3.2. A prepolymer (A-5) was obtained.
[合成例6]ホットメルトウレタンプレポリマー(A−6)の合成
温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた反応容器に、ポリカーボネートポリオール(日本ポリウレタン工業株式会社製「ニッポラン980R」、数平均分子量;2,600)を70質量部、ポリエステルポリオール(2)(ビスフェノールAのプロピレンオキシアド6モル付加物とセバシン酸との反応物、数平均分子量;2,000)を30質量部、を仕込み、減圧条件下で水分含有率が0.05質量%以下となるまで脱水した。
次いで、キシリレンジイソシアネートを25質量部を加え、100℃まで昇温して、イソシアネート基含有率が一定となるまで約3時間反応させて、NCO%;3.2のイソシアネート基を有するホットメルトウレタンプレポリマー(A−6)を得た。[Synthesis Example 6] Synthesis of Hot Melt Urethane Prepolymer (A-6) Polycarbonate polyol (manufactured by Nippon Polyurethane Industry Co., Ltd. "" in a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. NIPPOLAN 980R ", 70 parts by mass of number average molecular weight; 2,600), polyester polyol (2) (reaction product of bisphenol A propylene oxyad 6 mol adduct and sebacic acid, number average molecular weight: 2,000) 30 parts by mass were charged and dehydrated under reduced pressure until the water content was 0.05% by mass or less.
Next, 25 parts by mass of xylylene diisocyanate was added, the temperature was raised to 100 ° C., and the mixture was reacted for about 3 hours until the isocyanate group content became constant, and NCO%; hot melt urethane having an isocyanate group of 3.2 A prepolymer (A-6) was obtained.
[合成例7]ホットメルトウレタンプレポリマー(A−7)の合成
温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた反応容器に、ポリカーボネートポリオール(日本ポリウレタン工業株式会社製「ニッポラン980R」、数平均分子量;2,000)を70質量部、ポリエステルポリオール(2)(ビスフェノールAのプロピレンオキシアド6モル付加物とセバシン酸との反応物、数平均分子量;2,000)を30質量部、を仕込み、減圧条件下で水分含有率が0.05質量%以下となるまで脱水した。
次いで、4,4’−ジフェニルメタンジイソシアネートを25質量部を加え、100℃まで昇温して、イソシアネート基含有率が一定となるまで約3時間反応させて、NCO%;3.2のイソシアネート基を有するホットメルトウレタンプレポリマー(A−7)を得た。[Synthesis Example 7] Synthesis of Hot Melt Urethane Prepolymer (A-7) Polycarbonate polyol (manufactured by Nippon Polyurethane Industry Co., Ltd. "" in a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. NIPPOLAN 980R ”, 70 parts by mass of number average molecular weight; 2,000), polyester polyol (2) (reaction product of bisphenol A propylene oxyad 6 mol adduct and sebacic acid, number average molecular weight: 2,000) 30 parts by mass were charged and dehydrated under reduced pressure until the water content was 0.05% by mass or less.
Next, 25 parts by mass of 4,4′-diphenylmethane diisocyanate was added, the temperature was raised to 100 ° C., and the reaction was allowed to proceed for about 3 hours until the isocyanate group content became constant. A hot melt urethane prepolymer (A-7) was obtained.
[合成例8]ホットメルトウレタンプレポリマー(A−8)の合成
温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた反応容器に、ポリカーボネートポリオール(日本ポリウレタン工業株式会社製「ニッポラン980R」、数平均分子量;2,000)を70質量部、ポリエステルポリオール(1)(1,6−ヘキサンジオールとアジピン酸との反応物、数平均分子量;2,000)を30質量部、を仕込み、減圧条件下で水分含有率が0.05質量%以下となるまで脱水した。
次いで、キシリレンジイソシアネートを18質量部を加え、100℃まで昇温して、イソシアネート基含有率が一定となるまで約3時間反応させて、NCO%;3.2のイソシアネート基を有するホットメルトウレタンプレポリマー(A−8)を得た。[Synthesis Example 8] Synthesis of Hot Melt Urethane Prepolymer (A-8) Polycarbonate polyol (manufactured by Nippon Polyurethane Industry Co., Ltd. "" in a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. NIPPOLAN 980R ”, 70 parts by mass of number average molecular weight; 2,000), 30 parts by mass of polyester polyol (1) (reaction product of 1,6-hexanediol and adipic acid, number average molecular weight; 2,000), Was dehydrated under reduced pressure until the water content was 0.05% by mass or less.
Next, 18 parts by mass of xylylene diisocyanate was added, the temperature was raised to 100 ° C., and the reaction was allowed to proceed for about 3 hours until the isocyanate group content became constant, whereby a hot melt urethane having an isocyanate group of NCO%; 3.2. A prepolymer (A-8) was obtained.
[実施例1]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せて、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ45μmの発泡硬化物を得た。[Example 1]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot-melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, a polyethylene film with a thickness of 20 µm is pasted on the coated surface, and heated at 120 ° C for 5 minutes. Then, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foam cured product having a thickness of 45 μm.
[実施例2〜3]
湿気硬化型ホットメルトウレタン組成物の塗布する厚さを表1に示す通りに変更した以外は、実施例1と同様にして発泡硬化物を得た。[Examples 2-3]
A foamed cured product was obtained in the same manner as in Example 1 except that the thickness to which the moisture-curable hot melt urethane composition was applied was changed as shown in Table 1.
[実施例4]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「T−700」、数平均分子量;700)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−2)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。[Example 4]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“T-700” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 700), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and 2.2. The foaming agent composition (B-2) obtained by mixing 5 parts by mass was mixed with the molten hot-melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[実施例5]
ホットメルトウレタンプレポリマー(A−2)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−2)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。[Example 5]
100 parts by mass of hot-melt urethane prepolymer (A-2) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot melt urethane prepolymer (A-2), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[実施例6]
湿気硬化型ホットメルトウレタン組成物の塗布する厚さを表2に示す通りに変更した以外は、実施例5と同様にして発泡硬化物を得た。[Example 6]
A foam cured product was obtained in the same manner as in Example 5 except that the thickness of the moisture-curable hot melt urethane composition applied was changed as shown in Table 2.
[実施例7]
ホットメルトウレタンプレポリマー(A−3)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−3)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ45μmの発泡硬化物を得た。[Example 7]
100 parts by mass of hot-melt urethane prepolymer (A-3) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot-melt urethane prepolymer (A-3), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. After that, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foam cured product having a thickness of 45 μm.
[実施例8]
ホットメルトウレタンプレポリマー(A−4)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−4)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。[Example 8]
100 parts by mass of hot-melt urethane prepolymer (A-4) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot melt urethane prepolymer (A-4), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[実施例9]
ホットメルトウレタンプレポリマー(A−5)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−5)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ45μmの発泡硬化物を得た。[Example 9]
100 parts by mass of hot-melt urethane prepolymer (A-5) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot-melt urethane prepolymer (A-5), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. After that, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foam cured product having a thickness of 45 μm.
[実施例10]
ホットメルトウレタンプレポリマー(A−6)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−6)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。[Example 10]
100 parts by mass of hot-melt urethane prepolymer (A-6) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot melt urethane prepolymer (A-6), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[実施例11]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを1.5質量部、尿素を3.5質量部を混合して得た発泡剤組成物(B−3)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。[Example 11]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 1.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-3) obtained by mixing 3.5 parts by mass was mixed with the molten hot melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[実施例12]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを3.5質量部、尿素を1.5質量部を混合して得た発泡剤組成物(B−4)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ45μmの発泡硬化物を得た。[Example 12]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 3.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-4) obtained by mixing 1.5 parts by mass was mixed with the molten hot melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. After that, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foam cured product having a thickness of 45 μm.
[実施例13]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を10質量部、N,N’−ジニトロソペンタメチレンテトラミンを5質量部、尿素を5質量部を混合して得た発泡剤組成物(B−5)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。[Example 13]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 10 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and 5 parts by mass of urea The foaming agent composition (B-5) obtained by mixing the parts was mixed with the molten hot melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[実施例14]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、140℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ55μmの発泡硬化物を得た。[Example 14]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot-melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 140 ° C for 5 minutes. Then, it was left for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 55 μm.
[実施例15]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せて、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。[Example 15]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot melt urethane prepolymer (A-1), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, a polyethylene film with a thickness of 20 µm is pasted on the coated surface, and heated at 120 ° C for 5 minutes. Then, the mixture was allowed to stand for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foam cured product having a thickness of 50 μm.
[実施例16〜17]
湿気硬化型ホットメルトウレタン組成物の塗布する厚さを表1に示す通りに変更した以外は、実施例1と同様にして発泡硬化物を得た。[Examples 16 to 17]
A foamed cured product was obtained in the same manner as in Example 1 except that the thickness to which the moisture-curable hot melt urethane composition was applied was changed as shown in Table 1.
[実施例18]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「T−700」、数平均分子量;700)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−7)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ55μmの発泡硬化物を得た。[Example 18]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“T-700” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 700), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and 2.2. 5 parts by mass and a foaming agent composition (B-7) obtained by mixing 0.5 part by mass of boric acid are mixed with a molten hot melt urethane prepolymer (A-1), and a batch type agitator is used. Used and stirred.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 55 μm.
[実施例19]
ホットメルトウレタンプレポリマー(A−2)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−2)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ55μmの発泡硬化物を得た。[Example 19]
100 parts by mass of hot-melt urethane prepolymer (A-2) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot melt urethane prepolymer (A-2), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 55 μm.
[実施例20]
湿気硬化型ホットメルトウレタン組成物の塗布する厚さを表2に示す通りに変更した以外は、実施例5と同様にして発泡硬化物を得た。[Example 20]
A foam cured product was obtained in the same manner as in Example 5 except that the thickness of the moisture-curable hot melt urethane composition applied was changed as shown in Table 2.
[実施例21]
ホットメルトウレタンプレポリマー(A−3)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−3)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。[Example 21]
100 parts by mass of hot-melt urethane prepolymer (A-3) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot-melt urethane prepolymer (A-3), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[実施例22]
ホットメルトウレタンプレポリマー(A−4)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−4)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ55μmの発泡硬化物を得た。[Example 22]
100 parts by mass of hot-melt urethane prepolymer (A-4) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot-melt urethane prepolymer (A-4) and stirred in a batch system. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 55 μm.
[実施例23]
ホットメルトウレタンプレポリマー(A−5)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−5)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。[Example 23]
100 parts by mass of hot-melt urethane prepolymer (A-5) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot melt urethane prepolymer (A-5), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[実施例24]
ホットメルトウレタンプレポリマー(A−6)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−6)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ52μmの発泡硬化物を得た。[Example 24]
100 parts by mass of hot-melt urethane prepolymer (A-6) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot melt urethane prepolymer (A-6), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was allowed to stand for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foam cured product having a thickness of 52 μm.
[実施例25]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを1.5質量部、尿素を3.5質量部を、ホウ酸を0.5質量部混合して得た発泡剤組成物(B−8)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ55μmの発泡硬化物を得た。[Example 25]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 1.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea 3.5 parts by mass is mixed with a hot-melt urethane prepolymer (A-1) obtained by mixing a foaming agent composition (B-8) obtained by mixing 0.5 parts by mass of boric acid, and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 55 μm.
[実施例26]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを3.5質量部、尿素を1.5質量部を、ホウ酸を0.5質量部混合して得た発泡剤組成物(B−9)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ48μmの発泡硬化物を得た。[Example 26]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 3.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea 1.5 parts by mass is mixed with a hot-melt urethane prepolymer (A-1) obtained by mixing a foaming agent composition (B-9) obtained by mixing 0.5 part by mass of boric acid, and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was allowed to stand for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 48 μm.
[実施例27]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を10質量部、N,N’−ジニトロソペンタメチレンテトラミンを5質量部、尿素を5質量部を、ホウ酸を1.0質量部混合して得た発泡剤組成物(B−10)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ58μmの発泡硬化物を得た。[Example 27]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 10 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and 5 parts by mass of urea Part is mixed with a hot-melt urethane prepolymer (A-1) obtained by mixing a foaming agent composition (B-10) obtained by mixing 1.0 part by mass of boric acid, and a batch type stirrer is used. And stirred.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 58 μm.
[実施例28]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、140℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ60μmの発泡硬化物を得た。[Example 28]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot melt urethane prepolymer (A-1), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 140 ° C for 5 minutes. Thereafter, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 60 μm.
[実施例29]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を2.5質量部を混合して得た発泡剤組成物(B−11)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ60μmの発泡硬化物を得た。[Example 29]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea 2.5 parts by mass and a foaming agent composition (B-11) obtained by mixing 2.5 parts by mass of boric acid are mixed with a molten hot melt urethane prepolymer (A-1), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Thereafter, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 60 μm.
[比較例1]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、エチレングリコールを0.5質量部、N,N−ジメチルシクロヘキシルアミンを0.1質量部、水を0.1質量部混合して得た水発泡組成物(X−1)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、その後温度23℃、相対湿度65%の条件下で5日間放置し、厚さ32μmの発泡硬化物を得た。[Comparative Example 1]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, hot melted water foaming composition (X-1) obtained by mixing 0.5 parts by mass of ethylene glycol, 0.1 parts by mass of N, N-dimethylcyclohexylamine and 0.1 parts by mass of water It mixed with melt urethane prepolymer (A-1), and stirred using the batch type stirrer.
Immediately after that, a release paper (“ED100K” manufactured by Lintec Corporation) was applied to a thickness of 30 μm, and a 20 μm-thick polyethylene film was bonded onto the coated surface, and then a temperature of 23 ° C. and a relative humidity. The foamed cured product having a thickness of 32 μm was obtained by leaving it for 5 days under the condition of 65%.
[比較例2]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2質量部混合して得た発泡剤組成物(B’−1)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ40μmの発泡硬化物を得た。[Comparative Example 2]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Subsequently, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000) and 2 parts by mass of N, N′-dinitrosopentamethylenetetramine were obtained. The foaming agent composition (B′-1) was mixed with the molten hot melt urethane prepolymer (A-1) and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 40 μm.
[比較例3]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、尿素を2質量部混合して得た発泡剤組成物(B’−2)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ35μmの発泡硬化物を得た。[Comparative Example 3]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Subsequently, a blowing agent composition (B′-2) obtained by mixing 5 parts by mass of polyoxypropylenetriol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000) and 2 parts by mass of urea. ) Was mixed with the molten hot melt urethane prepolymer (A-1) and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 35 μm.
[比較例4]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、アゾジカルボンアミドを2.5質量部、尿素を2.5質量部混合して得た発泡剤組成物(B’−3)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ32μmの発泡硬化物を得た。[Comparative Example 4]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of azodicarbonamide, and 2.5 parts by mass of urea were mixed. The foaming agent composition (B′-3) obtained in this manner was mixed with the molten hot melt urethane prepolymer (A-1) and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. After that, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 32 μm.
[比較例5]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、4,4’−オキシビス(ベンゼンスルホニルヒドラジド)を2.5質量部、尿素を2.5質量部混合して得た発泡剤組成物(B’−4)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ33μmの発泡硬化物を得た。[Comparative Example 5]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of 4,4′-oxybis (benzenesulfonylhydrazide), urea The foaming agent composition (B′-4) obtained by mixing 2.5 parts by mass was mixed with the molten hot melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foam cured product having a thickness of 33 μm.
[比較例6]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、炭酸水素ナトリウムを2.5質量部、尿素を2.5質量部混合して得た発泡剤組成物(B’−5)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ32μmの発泡硬化物を得た。[Comparative Example 6]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of sodium bicarbonate, and 2.5 parts by mass of urea were mixed. The foaming agent composition (B′-5) obtained in this manner was mixed with the molten hot melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. After that, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 32 μm.
[溶融粘度の測定方法]
ホットメルトウレタンプレポリマー(A−1)〜(A−8)をそれぞれ100℃で1時間溶融した後に、1mlをサンプリングし、コーンプレート粘度計(M・S・Tエンジニアリング株式会社製デジタルコーンビスメーター「CV−1S RTタイプ」、40Pコーン、ローター回転数;50rpm)にて100℃における溶融粘度を測定した。[Measuring method of melt viscosity]
After each of the hot melt urethane prepolymers (A-1) to (A-8) was melted at 100 ° C. for 1 hour, 1 ml was sampled and a cone plate viscometer (digital cone vismeter manufactured by MST Engineering Co., Ltd.) The melt viscosity at 100 ° C. was measured with “CV-1S RT type”, 40P cone, rotor rotation speed: 50 rpm).
[発泡硬化物の発泡度の測定方法]
実施例及び比較例において、溶融したホットメルトウレタンプレポリマー(A)と発泡剤組成物(B)又は水発泡組成物(X)を添加した直後の体積(V1)と、発泡後の硬化物の体積(V2)とを測定し、その比(V2/V1)から発泡度を算出した。[Measurement method of foaming degree of foamed cured product]
In Examples and Comparative Examples, the volume (V 1 ) immediately after the melted hot-melt urethane prepolymer (A) and the foaming agent composition (B) or the water foaming composition (X) are added, and the cured product after foaming. The volume (V 2 ) was measured, and the degree of foaming was calculated from the ratio (V 2 / V 1 ).
[発泡状態の評価方法]
実施例及び比較例で得られた発泡硬化物及び硬化物を、日立ハイテクテクノロジー株式会社製走査型電子顕微鏡「SU3500」(倍率200倍)を使用して観察し、以下のように評価した。
「A」:良好な発泡状態が確認できる。
「B」:良好な発泡状態が確認できない。[Method for evaluating foaming state]
The foam hardened | cured material and hardened | cured material obtained by the Example and the comparative example were observed using the scanning electron microscope "SU3500" (magnification 200 times) by Hitachi High-Technology Co., Ltd., and evaluated as follows.
“A”: A good foaming state can be confirmed.
“B”: A good foaming state cannot be confirmed.
[風合いの評価方法]
実施例及び比較例で得られた発泡硬化物及び硬化物の風合いを触感により評価した。
「A」:極めて柔軟性に富み、凹凸が確認されない。
「B」:良好な柔軟性を有し、凹凸が確認されない。
「C」:硬い、又は、凹凸が確認される。[Texture evaluation method]
The foamed cured products and the textures of the cured products obtained in Examples and Comparative Examples were evaluated by touch.
“A”: Extremely flexible and unevenness is not confirmed.
“B”: Good flexibility and no irregularities are observed.
“C”: Hard or uneven.
[機械的物性の評価方法]
実施例及び比較例で得られた発泡硬化物及び硬化物を、長さ100mm及び幅5mmに裁断したものを試験片とした。この試験片の両端部をチャックで挟み、引張試験機「オートグラフAG−I」(株式会社島津製作所製)を用いて、温度23℃、湿度60%の雰囲気下で、クロスヘッドスピード300mm/分で引張り、試験片の100%モジュラス(MPa)、200%モジュラス(MPa)、破断点応力(MPa)、及び破断点伸度(%)を測定した。この時の標線間距離は20mm、チャック間の初期距離は20mmとした。なお、引張ることができず評価ができなかったものは「−」とした。[Mechanical properties evaluation method]
The foamed cured product and cured product obtained in the examples and comparative examples were cut into a length of 100 mm and a width of 5 mm as test pieces. Both ends of this test piece are sandwiched between chucks, and using a tensile tester “Autograph AG-I” (manufactured by Shimadzu Corporation), in an atmosphere at a temperature of 23 ° C. and a humidity of 60%, a crosshead speed of 300 mm / min The test piece was measured for 100% modulus (MPa), 200% modulus (MPa), stress at break (MPa), and elongation at break (%). At this time, the distance between the marked lines was 20 mm, and the initial distance between the chucks was 20 mm. In addition, the thing which was not able to be pulled and was not able to evaluate was set to "-".
表1〜5中の略語について説明する。
「PTMG」:ポリオキシテトラメチレングリコール(数平均分子量;2,000)
「PC」:ポリカーボネートポリオール(日本ポリウレタン工業株式会社製「ニッポラン980R」、数平均分子量;2,000)
「PEs(1)」:ポリエステルポリオール(1)(1,6−ヘキサンジオールとアジピン酸との反応物、数平均分子量;2,000)
「PEs(2)」:ポリエステルポリオール(2)(ビスフェノールAのプロピレンオキシアド6モル付加物とセバシン酸との反応物、数平均分子量;2,000)
「MDI」:4,4’−ジフェニルメタンジイソシアネート
「XDI」:キシリレンジイソシアネート
「MN3050」:ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)
「T700」:ポリオキシプロピレントリオール(三井化学株式会社製「T−700」、数平均分子量;700)Abbreviations in Tables 1 to 5 will be described.
“PTMG”: polyoxytetramethylene glycol (number average molecular weight; 2,000)
“PC”: Polycarbonate polyol (“Nipporan 980R” manufactured by Nippon Polyurethane Industry Co., Ltd., number average molecular weight; 2,000)
“PEs (1)”: Polyester polyol (1) (reaction product of 1,6-hexanediol and adipic acid, number average molecular weight; 2,000)
"PEs (2)": Polyester polyol (2) (reaction product of propylene oxyad 6 mol adduct of bisphenol A and sebacic acid, number average molecular weight; 2,000)
“MDI”: 4,4′-diphenylmethane diisocyanate “XDI”: xylylene diisocyanate “MN3050”: polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000)
“T700”: polyoxypropylene triol (“T-700” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 700)
本発明の湿気硬化型ホットメルトウレタン組成物は、図1及び2にも示す通り、薄膜でも良好な発泡状態を保持することができ、良好な風合いを有する発泡硬化物が得られることが分かった。また、機械的物性の低下も確認されなかった。
特に、発泡剤組成物(B)にホウ酸を用いた場合(実施例15〜29)には、優れた風合いを有する発泡硬化物が得られることが分かった。As shown in FIGS. 1 and 2, the moisture curable hot melt urethane composition of the present invention can maintain a good foamed state even in a thin film, and it is found that a foam cured product having a good texture can be obtained. . In addition, no decrease in mechanical properties was confirmed.
In particular, when boric acid was used for the foaming agent composition (B) (Examples 15 to 29), it was found that a foamed cured product having an excellent texture was obtained.
一方、比較例1は、水発泡法による発泡を検討したが、図3にも示す通り、水発泡による泡が残っておらず、(A)及び(B)成分の混合時に巻き込んだ泡のみが残存していた。良好な発泡状態を保持することできなかったことが確認された。また、これに起因して発泡硬化物の風合いも良好ではなかった。 On the other hand, Comparative Example 1 examined foaming by the water foaming method, but as shown in FIG. 3, there was no foam left by water foaming, and only the foams entrained during the mixing of the components (A) and (B). It remained. It was confirmed that a good foaming state could not be maintained. Further, due to this, the texture of the foamed cured product was not good.
比較例2は、発泡剤組成物(B)として尿素(b2)を用いなかった態様であるが、図4にも示す通り、発泡を制御できず、泡が基材に接触した形となり、得られた発泡硬化物の表面は凹凸が感じられ、風合いが不良であった。また、破断点伸度等の低下も確認された。 Comparative Example 2 is an embodiment in which urea (b2) was not used as the foaming agent composition (B), but as shown in FIG. 4, the foaming could not be controlled and the foam was in contact with the base material. The surface of the resulting foamed cured product had irregularities and a poor texture. In addition, a decrease in elongation at break etc. was also confirmed.
比較例3は、発泡剤組成物(B)としてN,N’−ジニトロソペンタメチレンテトラミン(b1)を用いなかった態様であるが、(A)及び(B)成分の混合時に巻き込んだ泡のみが残存していた。得られた発泡硬化物の風合いも良好ではなかった。 Comparative Example 3 is an embodiment in which N, N′-dinitrosopentamethylenetetramine (b1) was not used as the foaming agent composition (B), but only the bubbles involved during the mixing of the components (A) and (B). Remained. The texture of the obtained foamed cured product was not good.
比較例4〜6は、N,N’−ジニトロソペンタメチレンテトラミン(b1)の代わりにその他の熱分解性発泡剤を用いた態様であるが、図5にも示す通り、発生した泡が潰れていることが確認され、薄膜で良好な発泡状態を保持することができなかった。また、これに起因して発泡硬化物の風合いも良好ではなかった。 Comparative Examples 4 to 6 are embodiments in which other thermally decomposable foaming agents were used instead of N, N′-dinitrosopentamethylenetetramine (b1), but as shown in FIG. As a result, it was not possible to maintain a good foamed state with the thin film. Further, due to this, the texture of the foamed cured product was not good.
[作製例1]表皮層(iii−1)の作製
DIC株式会社製溶剤系ポリエーテル系ウレタン樹脂「クリスボン NB−130」100質量部に、DIC株式会社製顔料「DILAC BLACK L−6001」を20質量部、メチルエチルケトン/N,N−ジメチルホルムアミドの等量混合液を40質量部を混合し、コンマコーターを使用して、離型紙上に塗布量がwet換算で100g/m2となるように塗布した。その後、70℃で2分間、及び120℃で2分間乾燥させて、厚さ30μmの表皮層(iii−1)を作製。[Production Example 1] Production of skin layer (iii-1) To 100 parts by mass of solvent-based polyether urethane resin “Crisbon NB-130” manufactured by DIC Corporation, pigment “DILA BLACK L-6001” manufactured by DIC Corporation 20 40 parts by weight of a mixed solution of equal parts of methyl ethyl ketone / N, N-dimethylformamide is mixed with a comma coater so that the coating amount is 100 g / m 2 in terms of wet on the release paper. did. Then, it dried at 70 degreeC for 2 minutes and 120 degreeC for 2 minutes, and produced a 30-micrometer-thick skin layer (iii-1).
[作製例2]表皮層(iii−2)の作製
DIC株式会社製水系ポリエーテル系ウレタン樹脂「ハイドラン WLS−230」100質量部に、DIC株式会社製顔料「DILAC BLACK HS−9533」10質量部を混合し、コンマコーターを使用して、離型紙上に塗布量がwet換算で100g/m2となるように塗布した。その後、70℃で2分間、及び120℃で2分間乾燥させて、厚さ30μmの表皮層(iii−2)を作製した。[Production Example 2] Production of skin layer (iii-2) 100 parts by mass of water-based polyether urethane resin “Hydran WLS-230” manufactured by DIC Corporation, and 10 parts by mass of pigment “DIRAC BLACK HS-9533” manufactured by DIC Corporation And using a comma coater, it was coated on the release paper so that the coating amount was 100 g / m 2 in terms of wet. Then, it was dried at 70 ° C. for 2 minutes and at 120 ° C. for 2 minutes to produce a 30 μm-thick skin layer (iii-2).
[実施例30]
前記ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合攪拌して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−1)に2液混合撹拌機を使用して攪拌することで湿気硬化型ホットメルトウレタン組成物を得た。
次いで、得られた湿気硬化型ホットメルトウレタン組成物を前記表皮層(iii−1)上に、コンマコーターを使用して厚さ30μmとなるように塗布して、120℃で5分間加熱処理した後に、不織布を貼り合せ、その後、温度23℃、相対湿度65%の条件下で3日間放置し、中間層(ii)の厚さが45μmである合成皮革を得た。[Example 30]
100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea Moisture curing by stirring a hot-melt urethane prepolymer (A-1) obtained by mixing and stirring 2.5 parts by mass of a foaming agent composition (B-1) using a two-component mixing stirrer. Mold hot melt urethane composition was obtained.
Next, the obtained moisture-curable hot melt urethane composition was applied on the skin layer (iii-1) so as to have a thickness of 30 μm using a comma coater, and was heat-treated at 120 ° C. for 5 minutes. Thereafter, a nonwoven fabric was bonded, and then left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a synthetic leather having a thickness of the intermediate layer (ii) of 45 μm.
[実施例31〜40]
用いるホットメルトウレタンプレポリマー(A)、発泡剤組成物(B)、ホットメルトウレタンプレポリマー(A)の加熱溶融温度、表皮層(iii)、湿気硬化型ホットメルトウレタン組成物の塗布厚、及び後加熱の温度を表6〜7に示す通り変更した以外は、実施例30と同様にして合成皮革を得た。[Examples 31 to 40]
Hot melt urethane prepolymer (A) to be used, foaming agent composition (B), heat melting temperature of hot melt urethane prepolymer (A), skin layer (iii), coating thickness of moisture curable hot melt urethane composition, and Synthetic leather was obtained in the same manner as in Example 30 except that the post-heating temperature was changed as shown in Tables 6-7.
[実施例41]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合攪拌して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−1)に2液混合撹拌機を使用して撹拌することで湿気硬化型ホットメルトウレタン組成物を得た。
次いで、得られた湿気硬化型ホットメルトウレタン組成物を前記表皮層(iii−1)上に、コンマコーターを使用して厚さ30μmとなるように塗布して、120℃で5分間加熱処理した後に、不織布を貼り合せ、その後、温度23℃、相対湿度65%の条件下で3日間放置し、中間層(ii)の厚さが50μmである合成皮革を得た。[Example 41]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A two-component mixing stirrer was added to the hot melt urethane prepolymer (A-1) obtained by melting a foaming agent composition (B-6) obtained by mixing and stirring 2.5 parts by mass and 0.5 parts by mass of boric acid. A moisture-curing hot melt urethane composition was obtained by using and stirring.
Next, the obtained moisture-curable hot melt urethane composition was applied on the skin layer (iii-1) so as to have a thickness of 30 μm using a comma coater, and was heat-treated at 120 ° C. for 5 minutes. Thereafter, a nonwoven fabric was bonded, and then left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a synthetic leather having a thickness of the intermediate layer (ii) of 50 μm.
[実施例42〜56]
用いるホットメルトウレタンプレポリマー(A)、発泡剤組成物(B)、ホットメルトウレタンプレポリマー(A)の加熱溶融温度、表皮層(iii)、湿気硬化型ホットメルトウレタン組成物の塗布厚、及び後加熱の温度を表7〜9に示す通り変更した以外は、実施例41と同様にして合成皮革を得た。[Examples 42 to 56]
Hot melt urethane prepolymer (A) to be used, foaming agent composition (B), heat melting temperature of hot melt urethane prepolymer (A), skin layer (iii), coating thickness of moisture curable hot melt urethane composition, and A synthetic leather was obtained in the same manner as in Example 41 except that the post-heating temperature was changed as shown in Tables 7-9.
[実施例57]
前記ホットメルトウレタンプレポリマー(A−3)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合攪拌して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−3)に2液混合撹拌機を使用して攪拌することで湿気硬化型ホットメルトウレタン組成物を得た。
次いで、得られた湿気硬化型ホットメルトウレタン組成物を前記表皮層(iii−1)上に、コンマコーターを使用して厚さ30μmとなるように塗布して、120℃で5分間加熱処理した後に、不織布を貼り合せ、その後、温度23℃、相対湿度65%の条件下で3日間放置し、中間層(ii)の厚さが45μmである合成皮革を得た。[Example 57]
100 parts by mass of the hot melt urethane prepolymer (A-3) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea Moisture curing by stirring a hot-melt urethane prepolymer (A-3) obtained by mixing and stirring 2.5 parts by mass of a foaming agent composition (B-1) using a two-component mixing stirrer Mold hot melt urethane composition was obtained.
Next, the obtained moisture-curable hot melt urethane composition was applied on the skin layer (iii-1) so as to have a thickness of 30 μm using a comma coater, and was heat-treated at 120 ° C. for 5 minutes. Thereafter, a nonwoven fabric was bonded, and then left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a synthetic leather having a thickness of the intermediate layer (ii) of 45 μm.
[実施例58〜67]
用いるホットメルトウレタンプレポリマー(A)、発泡剤組成物(B)、ホットメルトウレタンプレポリマー(A)の加熱溶融温度、表皮層(iii)、湿気硬化型ホットメルトウレタン組成物の塗布厚、及び後加熱の温度を表10〜11に示す通り変更した以外は、実施例57と同様にして合成皮革を得た。[Examples 58 to 67]
Hot melt urethane prepolymer (A) to be used, foaming agent composition (B), heat melting temperature of hot melt urethane prepolymer (A), skin layer (iii), coating thickness of moisture curable hot melt urethane composition, and Synthetic leather was obtained in the same manner as in Example 57 except that the post-heating temperature was changed as shown in Tables 10 to 11.
[実施例68]
ホットメルトウレタンプレポリマー(A−3)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合攪拌して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−3)に2液混合撹拌機を使用して攪拌することで湿気硬化型ホットメルトウレタン組成物を得た。
次いで、得られた湿気硬化型ホットメルトウレタン組成物を前記表皮層(iii−1)上に、コンマコーターを使用して厚さ30μmとなるように塗布して、120℃で5分間加熱処理した後に、不織布を貼り合せ、その後、温度23℃、相対湿度65%の条件下で3日間放置し、中間層(ii)の厚さが50μmである合成皮革を得た。[Example 68]
100 parts by mass of hot-melt urethane prepolymer (A-3) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A two-component mixing stirrer is added to a hot melt urethane prepolymer (A-3) obtained by melting a foaming agent composition (B-6) obtained by mixing and stirring 2.5 parts by mass and 0.5 parts by mass of boric acid. A moisture-curing hot melt urethane composition was obtained by using and stirring.
Next, the obtained moisture-curable hot melt urethane composition was applied on the skin layer (iii-1) so as to have a thickness of 30 μm using a comma coater, and was heat-treated at 120 ° C. for 5 minutes. Thereafter, a nonwoven fabric was bonded, and then left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a synthetic leather having a thickness of the intermediate layer (ii) of 50 μm.
[実施例69〜83]
用いるホットメルトウレタンプレポリマー(A)、発泡剤組成物(B)、ホットメルトウレタンプレポリマー(A)の加熱溶融温度、表皮層(iii)、湿気硬化型ホットメルトウレタン組成物の塗布厚、及び後加熱の温度を表11〜13に示す通り変更した以外は、実施例68と同様にして合成皮革を得た。[Examples 69 to 83]
Hot melt urethane prepolymer (A) to be used, foaming agent composition (B), heat melting temperature of hot melt urethane prepolymer (A), skin layer (iii), coating thickness of moisture curable hot melt urethane composition, and A synthetic leather was obtained in the same manner as in Example 68 except that the post-heating temperature was changed as shown in Tables 11-13.
[比較例7]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、エチレングリコールを0.5質量部、N,N−ジメチルシクロヘキシルアミンを0.1質量部、水を0.1質量部混合して得た水発泡組成物(X−1)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、2液混合撹拌機を使用して撹拌して、湿気硬化型ホットメルトウレタン組成物を得た。
その後、前記表皮層(iii−1)上に、コンマコーターを使用して厚さ30μmとなるように塗布して、該塗布面上に不織布を貼り合せ、その後温度23℃、相対湿度65%の条件下で5日間放置し、中間層(ii)の厚さが32μmである合成皮革を得た。[Comparative Example 7]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, hot melted water foaming composition (X-1) obtained by mixing 0.5 parts by mass of ethylene glycol, 0.1 parts by mass of N, N-dimethylcyclohexylamine and 0.1 parts by mass of water It mixed with melt urethane prepolymer (A-1), and it stirred using the 2 liquid mixing stirrer, and obtained the moisture hardening type hot melt urethane composition.
Then, on the skin layer (iii-1), using a comma coater, it was applied so as to have a thickness of 30 μm, and a non-woven fabric was bonded on the coated surface, and then the temperature was 23 ° C. and the relative humidity was 65%. The synthetic leather with the thickness of the intermediate layer (ii) of 32 μm was obtained by leaving it under conditions for 5 days.
[比較例8]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部混合して得た発泡剤組成物(B’−1)を溶融したホットメルトウレタンプレポリマー(A−1)に2液混合撹拌機を使用して撹拌することで湿気硬化型ホットメルトウレタン組成物を得た。
次いで、得られた湿気硬化型ホットメルトウレタン組成物を前記表皮層(iii−1)上に、コンマコーターを使用して厚さ30μmとなるように塗布して、120℃で5分間加熱処理した後に、不織布を貼り合せ、その後、温度23℃、相対湿度65%の条件下で3日間放置し、中間層(ii)の厚さが40μmである合成皮革を得た。[Comparative Example 8]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000) and 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine were mixed. A moisture-curable hot melt urethane composition was obtained by stirring the obtained foaming agent composition (B′-1) with a hot melt urethane prepolymer (A-1) using a two-component mixing stirrer. .
Next, the obtained moisture-curable hot melt urethane composition was applied on the skin layer (iii-1) so as to have a thickness of 30 μm using a comma coater, and was heat-treated at 120 ° C. for 5 minutes. Thereafter, a nonwoven fabric was bonded, and then left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a synthetic leather having a thickness of the intermediate layer (ii) of 40 μm.
[比較例9〜12]
用いるホットメルトウレタンプレポリマー(A)、発泡剤組成物(B)、ホットメルトウレタンプレポリマー(A)の加熱溶融温度、表皮層(iii)、湿気硬化型ホットメルトウレタン組成物の塗布厚、及び後加熱の温度を表14に示す通り変更した以外は、比較例2と同様にして合成皮革を得た。[Comparative Examples 9-12]
Hot melt urethane prepolymer (A) to be used, foaming agent composition (B), heat melting temperature of hot melt urethane prepolymer (A), skin layer (iii), coating thickness of moisture curable hot melt urethane composition, and A synthetic leather was obtained in the same manner as in Comparative Example 2 except that the post-heating temperature was changed as shown in Table 14.
[中間層(ii)の発泡度の測定方法]
実施例及び比較例において、溶融したホットメルトウレタンプレポリマー(A)と発泡剤組成物(B)又は水発泡組成物(X)を添加した直後の体積(V1)と、発泡後の硬化物の体積(V2)とを測定し、その比(V2/V1)から発泡度を算出した。[Method for Measuring Foaming Level of Intermediate Layer (ii)]
In Examples and Comparative Examples, the volume (V 1 ) immediately after the melted hot-melt urethane prepolymer (A) and the foaming agent composition (B) or the water foaming composition (X) are added, and the cured product after foaming. The volume (V 2 ) was measured, and the degree of foaming was calculated from the ratio (V 2 / V 1 ).
[発泡状態の評価方法]
実施例及び比較例で得られた合成皮革の中間層(ii)を、日立ハイテクテクノロジー株式会社製走査型電子顕微鏡「SU3500」(倍率200倍)を使用して観察し、以下のように評価した。
「A」:良好な発泡状態が確認できる。
「B」:良好な発泡状態が確認できない。[Method for evaluating foaming state]
The synthetic leather intermediate layer (ii) obtained in Examples and Comparative Examples was observed using a scanning electron microscope “SU3500” (200 × magnification) manufactured by Hitachi High-Technologies Corporation and evaluated as follows. .
“A”: A good foaming state can be confirmed.
“B”: A good foaming state cannot be confirmed.
[風合いの評価方法]
実施例及び比較例で得られた合成皮革の風合いを触感により評価した。
「A」:極めて柔軟性に富み、凹凸が確認されない。
「B」:良好な柔軟性を有し、凹凸が確認されない。
「C」:硬い、又は、凹凸が確認される。[Texture evaluation method]
The texture of the synthetic leather obtained in the examples and comparative examples was evaluated by touch.
“A”: Extremely flexible and unevenness is not confirmed.
“B”: Good flexibility and no irregularities are observed.
“C”: Hard or uneven.
[耐加水分解性の評価方法]
実施例30〜56、及び比較例7〜12で得られた合成皮革の表皮層上に、ホットメルト布テープを130℃に5秒かけて接着した後に、テンシロン(オリエンテック株式会社製テンシロン万能試験機「RTC−1210A」)を使用して、クロスヘッド測度;200mm/分の条件で剥離強度を測定し、常態での剥離強度とした。
次に、実施例及び比較例で得られた合成皮革を、温度70℃、湿度95%の条件下で5週間放置した後に、同様に剥離強度を測定し、耐加水分解試験後の剥離強度とした。[Method for evaluating hydrolysis resistance]
After bonding the hot melt cloth tape to 130 ° C. over 5 seconds on the skin layer of the synthetic leather obtained in Examples 30 to 56 and Comparative Examples 7 to 12, Tensilon (Tensilon Universal Test manufactured by Orientec Co., Ltd.) Machine “RTC-1210A”), the peel strength was measured under the condition of a crosshead measurement: 200 mm / min, and the peel strength in the normal state was obtained.
Next, the synthetic leather obtained in Examples and Comparative Examples was allowed to stand for 5 weeks under conditions of a temperature of 70 ° C. and a humidity of 95%, and then the peel strength was measured in the same manner, and the peel strength after the hydrolysis resistance test and did.
[耐屈曲性の評価方法]
実施例30〜56、及び比較例7〜12で得られた合成皮革を、株式会社東洋精機製作所製「MIT屈曲試験機」を使用し、常温(23℃)で30万回の屈曲試験、及び低温(−10℃)で10万回の屈曲試験をして表面に亀裂が入らなければ「T」、試験途中で亀裂が入った場合は、その時の屈曲回数を表に示す。
次に、実施例及び比較例で得られた合成皮革を、温度70℃、湿度95%の条件下で5週間放置した後に、同様に耐屈曲性試験を測定し、耐加水分解試験後の耐屈曲性も同様に評価した。[Bend resistance evaluation method]
The synthetic leather obtained in Examples 30 to 56 and Comparative Examples 7 to 12 was subjected to 300,000 bending tests at room temperature (23 ° C.) using “MIT bending tester” manufactured by Toyo Seiki Seisakusho Co., Ltd. If the surface is not cracked 100,000 times at a low temperature (−10 ° C.), “T”. If the surface is cracked, the number of times of bending is shown in the table.
Next, the synthetic leathers obtained in the examples and comparative examples were allowed to stand for 5 weeks under conditions of a temperature of 70 ° C. and a humidity of 95%, and then the flex resistance test was measured in the same manner, and the resistance to resistance after the hydrolysis test was measured. Flexibility was similarly evaluated.
[耐久性の評価方法]
実施例57〜83で得られた合成皮革の表皮層上に、ホットメルト布テープを130℃に5秒かけて接着した後に、テンシロン(オリエンテック株式会社製テンシロン万能試験機「RTC−1210A」)を使用して、クロスヘッド測度;200mm/分の条件で剥離強度を測定し、常態での剥離強度とした。
次に、実施例及び比較例で得られた合成皮革を、温度70℃、湿度95%の条件下で5週間放置した後に、同様に剥離強度を測定し、耐加水分解試験後の剥離強度とした。
更に、実施例及び比較例で得られた合成皮革を、温度120℃の条件下で500時間放置した後に、同様に剥離強度を測定し、耐熱試験後の剥離強度とした。[Durability evaluation method]
After adhering the hot melt cloth tape to 130 ° C. over 5 seconds on the skin layer of the synthetic leather obtained in Examples 57 to 83, Tensilon (Tensilon Universal Testing Machine “RTC-1210A” manufactured by Orientec Co., Ltd.) Was used to measure the peel strength under the condition of a crosshead measurement; 200 mm / min.
Next, the synthetic leather obtained in Examples and Comparative Examples was allowed to stand for 5 weeks under conditions of a temperature of 70 ° C. and a humidity of 95%, and then the peel strength was measured in the same manner, and the peel strength after the hydrolysis resistance test and did.
Furthermore, the synthetic leather obtained in Examples and Comparative Examples was allowed to stand for 500 hours at a temperature of 120 ° C., and then the peel strength was measured in the same manner as the peel strength after the heat test.
実施例30〜56は、ポリオキシテトラメチレングリコールをポリオールの主成分として使用したホットメルトウレタンプレポリマーを用いて製造した合成皮革であるが、合成皮革の中間層の形成にDMF等の有機溶剤を一切使用せず、かつ、中間層が薄膜である場合でも良好な発泡状態を保持することができることが分かった。また、本発明の合成皮革は、風合い、耐屈曲性、及び耐加水分解性にも優れるものであった。 Examples 30 to 56 are synthetic leathers produced using a hot melt urethane prepolymer using polyoxytetramethylene glycol as the main component of polyol, but an organic solvent such as DMF is used to form an intermediate layer of the synthetic leather. It was found that a good foamed state can be maintained even when no intermediate layer is used and the intermediate layer is a thin film. In addition, the synthetic leather of the present invention was excellent in texture, flex resistance, and hydrolysis resistance.
また、実施例57〜83は、ポリカーボネートポリオールをポリオールの主成分として使用したホットメルトウレタンプレポリマーを用いて製造した合成皮革であるが、合成皮革の中間層の形成にDMF等の有機溶剤を一切使用せず、かつ、中間層が薄膜である場合でも良好な発泡状態を保持することができることが分かった。また、本発明の合成皮革は、風合い、及び耐久性にも優れるものであった。 Examples 57 to 83 are synthetic leathers produced using a hot melt urethane prepolymer using polycarbonate polyol as the main component of polyol, but no organic solvent such as DMF is used to form an intermediate layer of synthetic leather. It was found that a good foamed state could be maintained even when not used and the intermediate layer was a thin film. Further, the synthetic leather of the present invention was excellent in texture and durability.
一方、比較例7は、水発泡法による発泡を検討したが、発泡度が小さく、良好な発泡状態を保持することできなかった。これはホットメルトウレタンプレポリマーと水発泡組成物との混合時に巻き込んだ泡のみが残存していたと考えられる。また、これに起因して合成皮革の風合いも良好ではなかった。 On the other hand, Comparative Example 7 examined foaming by the water foaming method, but the foaming degree was small and a good foaming state could not be maintained. It is considered that only bubbles entrained during mixing of the hot melt urethane prepolymer and the water foam composition remained. Also, due to this, the texture of the synthetic leather was not good.
比較例8は、発泡剤組成物(B)として尿素(b2)を用いなかった態様であるが、発泡を制御できず、得られた合成皮革の表面は凹凸が感じられ、風合いが不良であった。 Comparative Example 8 is an embodiment in which urea (b2) was not used as the foaming agent composition (B), but foaming could not be controlled, and the surface of the obtained synthetic leather was felt uneven and the texture was poor. It was.
比較例9は、発泡剤組成物(B)としてN,N’−ジニトロソペンタメチレンテトラミン(b1)を用いなかった態様であるが、発泡度が小さく、(A)及び(B)成分の混合時に巻き込んだ泡のみが残存していたと考えられる。得られた合成皮革の風合いも不良であった。 Comparative Example 9 is an embodiment in which N, N′-dinitrosopentamethylenetetramine (b1) was not used as the foaming agent composition (B), but the degree of foaming was small, and mixing of components (A) and (B) It is thought that only the bubbles that were sometimes involved remained. The texture of the obtained synthetic leather was also poor.
比較例10〜12は、N,N’−ジニトロソペンタメチレンテトラミン(b1)の代わりにその他の熱分解性発泡剤を用いた態様であるが、発泡度が小さく、薄膜で良好な発泡状態を保持することができなかった。また、これに起因して合成皮革の風合いも良好ではなかった。 Comparative Examples 10 to 12 are embodiments in which other thermally decomposable foaming agents are used instead of N, N′-dinitrosopentamethylenetetramine (b1), but the foaming degree is small and a good foaming state is obtained with a thin film. Could not hold. Also, due to this, the texture of the synthetic leather was not good.
[参考例1]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せて、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ45μmの発泡硬化物を得た。
[ Reference Example 1]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot-melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, a polyethylene film with a thickness of 20 µm is pasted on the coated surface, and heated at 120 ° C for 5 minutes. Then, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foam cured product having a thickness of 45 μm.
[参考例2〜3]
湿気硬化型ホットメルトウレタン組成物の塗布する厚さを表1に示す通りに変更した以外は、実施例1と同様にして発泡硬化物を得た。
[ Reference Examples 2-3]
A foamed cured product was obtained in the same manner as in Example 1 except that the thickness to which the moisture-curable hot melt urethane composition was applied was changed as shown in Table 1.
[参考例4]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「T−700」、数平均分子量;700)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−2)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。
[ Reference Example 4]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“T-700” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 700), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and 2.2. The foaming agent composition (B-2) obtained by mixing 5 parts by mass was mixed with the molten hot-melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[参考例5]
ホットメルトウレタンプレポリマー(A−2)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−2)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。
[ Reference Example 5]
100 parts by mass of hot-melt urethane prepolymer (A-2) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot melt urethane prepolymer (A-2), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[参考例6]
湿気硬化型ホットメルトウレタン組成物の塗布する厚さを表2に示す通りに変更した以外は、実施例5と同様にして発泡硬化物を得た。
[ Reference Example 6]
A foam cured product was obtained in the same manner as in Example 5 except that the thickness of the moisture-curable hot melt urethane composition applied was changed as shown in Table 2.
[参考例7]
ホットメルトウレタンプレポリマー(A−3)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−3)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ45μmの発泡硬化物を得た。
[ Reference Example 7]
100 parts by mass of hot-melt urethane prepolymer (A-3) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot-melt urethane prepolymer (A-3), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. After that, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foam cured product having a thickness of 45 μm.
[参考例8]
ホットメルトウレタンプレポリマー(A−4)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−4)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。
[ Reference Example 8]
100 parts by mass of hot-melt urethane prepolymer (A-4) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot melt urethane prepolymer (A-4), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[参考例9]
ホットメルトウレタンプレポリマー(A−5)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−5)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ45μmの発泡硬化物を得た。
[ Reference Example 9]
100 parts by mass of hot-melt urethane prepolymer (A-5) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot-melt urethane prepolymer (A-5), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. After that, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foam cured product having a thickness of 45 μm.
[参考例10]
ホットメルトウレタンプレポリマー(A−6)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−6)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。
[ Reference Example 10]
100 parts by mass of hot-melt urethane prepolymer (A-6) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot melt urethane prepolymer (A-6), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[参考例11]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを1.5質量部、尿素を3.5質量部を混合して得た発泡剤組成物(B−3)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。
[ Reference Example 11]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 1.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-3) obtained by mixing 3.5 parts by mass was mixed with the molten hot melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[参考例12]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを3.5質量部、尿素を1.5質量部を混合して得た発泡剤組成物(B−4)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ45μmの発泡硬化物を得た。
[ Reference Example 12]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 3.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-4) obtained by mixing 1.5 parts by mass was mixed with the molten hot melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. After that, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foam cured product having a thickness of 45 μm.
[参考例13]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を10質量部、N,N’−ジニトロソペンタメチレンテトラミンを5質量部、尿素を5質量部を混合して得た発泡剤組成物(B−5)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。
[ Reference Example 13]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 10 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and 5 parts by mass of urea The foaming agent composition (B-5) obtained by mixing the parts was mixed with the molten hot melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[参考例14]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、140℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ55μmの発泡硬化物を得た。
[ Reference Example 14]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea The foaming agent composition (B-1) obtained by mixing 2.5 parts by mass was mixed with the molten hot-melt urethane prepolymer (A-1), and stirred using a batch type stirrer.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 140 ° C for 5 minutes. Then, it was left for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 55 μm.
[実施例1]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せて、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。
[Example 1]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot melt urethane prepolymer (A-1), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, a polyethylene film with a thickness of 20 µm is pasted on the coated surface, and heated at 120 ° C for 5 minutes. Then, the mixture was allowed to stand for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foam cured product having a thickness of 50 μm.
[実施例2〜3]
湿気硬化型ホットメルトウレタン組成物の塗布する厚さを表1に示す通りに変更した以外は、実施例1と同様にして発泡硬化物を得た。
[Examples 2 to 3 ]
A foamed cured product was obtained in the same manner as in Example 1 except that the thickness to which the moisture-curable hot melt urethane composition was applied was changed as shown in Table 1.
[実施例4]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「T−700」、数平均分子量;700)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−7)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ55μmの発泡硬化物を得た。
[Example 4 ]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“T-700” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 700), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and 2.2. 5 parts by mass and a foaming agent composition (B-7) obtained by mixing 0.5 part by mass of boric acid are mixed with a molten hot melt urethane prepolymer (A-1), and a batch type agitator is used. Used and stirred.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 55 μm.
[実施例5]
ホットメルトウレタンプレポリマー(A−2)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−2)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ55μmの発泡硬化物を得た。
[Example 5 ]
100 parts by mass of hot-melt urethane prepolymer (A-2) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot melt urethane prepolymer (A-2), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 55 μm.
[実施例6]
湿気硬化型ホットメルトウレタン組成物の塗布する厚さを表2に示す通りに変更した以外は、実施例5と同様にして発泡硬化物を得た。
[Example 6 ]
A foam cured product was obtained in the same manner as in Example 5 except that the thickness of the moisture-curable hot melt urethane composition applied was changed as shown in Table 2.
[実施例7]
ホットメルトウレタンプレポリマー(A−3)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−3)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。
[Example 7 ]
100 parts by mass of hot-melt urethane prepolymer (A-3) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot-melt urethane prepolymer (A-3), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[実施例8]
ホットメルトウレタンプレポリマー(A−4)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−4)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ55μmの発泡硬化物を得た。
[Example 8 ]
100 parts by mass of hot-melt urethane prepolymer (A-4) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot-melt urethane prepolymer (A-4) and stirred in a batch system. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 55 μm.
[実施例9]
ホットメルトウレタンプレポリマー(A−5)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−5)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ50μmの発泡硬化物を得た。
[Example 9 ]
100 parts by mass of hot-melt urethane prepolymer (A-5) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot melt urethane prepolymer (A-5), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 50 μm.
[実施例10]
ホットメルトウレタンプレポリマー(A−6)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−6)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ52μmの発泡硬化物を得た。
[Example 10 ]
100 parts by mass of hot-melt urethane prepolymer (A-6) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot melt urethane prepolymer (A-6), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was allowed to stand for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foam cured product having a thickness of 52 μm.
[実施例11]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを1.5質量部、尿素を3.5質量部を、ホウ酸を0.5質量部混合して得た発泡剤組成物(B−8)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ55μmの発泡硬化物を得た。
[Example 11 ]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 1.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea 3.5 parts by mass is mixed with a hot-melt urethane prepolymer (A-1) obtained by mixing a foaming agent composition (B-8) obtained by mixing 0.5 parts by mass of boric acid, and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 55 μm.
[実施例12]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを3.5質量部、尿素を1.5質量部を、ホウ酸を0.5質量部混合して得た発泡剤組成物(B−9)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ48μmの発泡硬化物を得た。
[Example 12 ]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 3.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea 1.5 parts by mass is mixed with a hot-melt urethane prepolymer (A-1) obtained by mixing a foaming agent composition (B-9) obtained by mixing 0.5 part by mass of boric acid, and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was allowed to stand for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 48 μm.
[実施例13]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を10質量部、N,N’−ジニトロソペンタメチレンテトラミンを5質量部、尿素を5質量部を、ホウ酸を1.0質量部混合して得た発泡剤組成物(B−10)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ58μmの発泡硬化物を得た。
[Example 13 ]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 10 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and 5 parts by mass of urea Part is mixed with a hot-melt urethane prepolymer (A-1) obtained by mixing a foaming agent composition (B-10) obtained by mixing 1.0 part by mass of boric acid, and a batch type stirrer is used. And stirred.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Then, it was left for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 58 μm.
[実施例14]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、140℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ60μmの発泡硬化物を得た。
[Example 14 ]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A foaming agent composition (B-6) obtained by mixing 2.5 parts by mass and 0.5 parts by mass of boric acid is mixed with a molten hot melt urethane prepolymer (A-1), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 140 ° C for 5 minutes. Thereafter, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 60 μm.
[実施例15]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を2.5質量部を混合して得た発泡剤組成物(B−11)を溶融したホットメルトウレタンプレポリマー(A−1)に混合し、バッチ式の撹拌機を使用して撹拌した。
その後、直ちに離型紙(リンテック株式会社製「ED100K」)の上に、厚さ30μmとなるように塗布して、該塗布面上に厚み20μmのポリエチレンフィルムを貼り合せ、120℃で5分間加熱処理し、その後温度23℃、相対湿度65%の条件下で3日間放置し、厚さ60μmの発泡硬化物を得た。
[Example 15 ]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea 2.5 parts by mass and a foaming agent composition (B-11) obtained by mixing 2.5 parts by mass of boric acid are mixed with a molten hot melt urethane prepolymer (A-1), and batch-type stirring is performed. Stir using the machine.
Immediately after that, it is applied on release paper ("ED100K" manufactured by Lintec Corporation) to a thickness of 30 µm, and a polyethylene film with a thickness of 20 µm is pasted on the coated surface, followed by heat treatment at 120 ° C for 5 minutes. Thereafter, it was allowed to stand for 3 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a foamed cured product having a thickness of 60 μm.
[表1]
[Table 1]
[表2]
[Table 2]
[表3]
[Table 3]
[表4]
[Table 4]
[表5]
[Table 5]
[参考例15]
前記ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合攪拌して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−1)に2液混合撹拌機を使用して攪拌することで湿気硬化型ホットメルトウレタン組成物を得た。
次いで、得られた湿気硬化型ホットメルトウレタン組成物を前記表皮層(iii−1)上に、コンマコーターを使用して厚さ30μmとなるように塗布して、120℃で5分間加熱処理した後に、不織布を貼り合せ、その後、温度23℃、相対湿度65%の条件下で3日間放置し、中間層(ii)の厚さが45μmである合成皮革を得た。
[ Reference Example 15 ]
100 parts by mass of the hot melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea Moisture curing by stirring a hot-melt urethane prepolymer (A-1) obtained by mixing and stirring 2.5 parts by mass of a foaming agent composition (B-1) using a two-component mixing stirrer. Mold hot melt urethane composition was obtained.
Next, the obtained moisture-curable hot melt urethane composition was applied on the skin layer (iii-1) so as to have a thickness of 30 μm using a comma coater, and was heat-treated at 120 ° C. for 5 minutes. Thereafter, a nonwoven fabric was bonded, and then left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a synthetic leather having a thickness of the intermediate layer (ii) of 45 μm.
[参考例16〜25]
用いるホットメルトウレタンプレポリマー(A)、発泡剤組成物(B)、ホットメルトウレタンプレポリマー(A)の加熱溶融温度、表皮層(iii)、湿気硬化型ホットメルトウレタン組成物の塗布厚、及び後加熱の温度を表6〜7に示す通り変更した以外は、実施例30と同様にして合成皮革を得た。
[ Reference Examples 16 to 25 ]
Hot melt urethane prepolymer (A) to be used, foaming agent composition (B), heat melting temperature of hot melt urethane prepolymer (A), skin layer (iii), coating thickness of moisture curable hot melt urethane composition, and Synthetic leather was obtained in the same manner as in Example 30 except that the post-heating temperature was changed as shown in Tables 6-7.
[実施例16]
ホットメルトウレタンプレポリマー(A−1)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合攪拌して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−1)に2液混合撹拌機を使用して撹拌することで湿気硬化型ホットメルトウレタン組成物を得た。
次いで、得られた湿気硬化型ホットメルトウレタン組成物を前記表皮層(iii−1)上に、コンマコーターを使用して厚さ30μmとなるように塗布して、120℃で5分間加熱処理した後に、不織布を貼り合せ、その後、温度23℃、相対湿度65%の条件下で3日間放置し、中間層(ii)の厚さが50μmである合成皮革を得た。
[Example 16 ]
100 parts by mass of hot-melt urethane prepolymer (A-1) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A two-component mixing stirrer was added to the hot melt urethane prepolymer (A-1) obtained by melting a foaming agent composition (B-6) obtained by mixing and stirring 2.5 parts by mass and 0.5 parts by mass of boric acid. A moisture-curing hot melt urethane composition was obtained by using and stirring.
Next, the obtained moisture-curable hot melt urethane composition was applied on the skin layer (iii-1) so as to have a thickness of 30 μm using a comma coater, and was heat-treated at 120 ° C. for 5 minutes. Thereafter, a nonwoven fabric was bonded, and then left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a synthetic leather having a thickness of the intermediate layer (ii) of 50 μm.
[実施例17〜29、参考例26〜27]
用いるホットメルトウレタンプレポリマー(A)、発泡剤組成物(B)、ホットメルトウレタンプレポリマー(A)の加熱溶融温度、表皮層(iii)、湿気硬化型ホットメルトウレタン組成物の塗布厚、及び後加熱の温度を表7〜9に示す通り変更した以外は、実施例41と同様にして合成皮革を得た。
[Examples 17 to 29, Reference Examples 26 to 27 ]
Hot melt urethane prepolymer (A) to be used, foaming agent composition (B), heat melting temperature of hot melt urethane prepolymer (A), skin layer (iii), coating thickness of moisture curable hot melt urethane composition, and A synthetic leather was obtained in the same manner as in Example 41 except that the post-heating temperature was changed as shown in Tables 7-9.
[参考例28]
前記ホットメルトウレタンプレポリマー(A−3)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部を混合攪拌して得た発泡剤組成物(B−1)を溶融したホットメルトウレタンプレポリマー(A−3)に2液混合撹拌機を使用して攪拌することで湿気硬化型ホットメルトウレタン組成物を得た。
次いで、得られた湿気硬化型ホットメルトウレタン組成物を前記表皮層(iii−1)上に、コンマコーターを使用して厚さ30μmとなるように塗布して、120℃で5分間加熱処理した後に、不織布を貼り合せ、その後、温度23℃、相対湿度65%の条件下で3日間放置し、中間層(ii)の厚さが45μmである合成皮革を得た。
[ Reference Example 28 ]
100 parts by mass of the hot melt urethane prepolymer (A-3) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea Moisture curing by stirring a hot-melt urethane prepolymer (A-3) obtained by mixing and stirring 2.5 parts by mass of a foaming agent composition (B-1) using a two-component mixing stirrer Mold hot melt urethane composition was obtained.
Next, the obtained moisture-curable hot melt urethane composition was applied on the skin layer (iii-1) so as to have a thickness of 30 μm using a comma coater, and was heat-treated at 120 ° C. for 5 minutes. Thereafter, a nonwoven fabric was bonded, and then left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a synthetic leather having a thickness of the intermediate layer (ii) of 45 μm.
[参考例29〜38]
用いるホットメルトウレタンプレポリマー(A)、発泡剤組成物(B)、ホットメルトウレタンプレポリマー(A)の加熱溶融温度、表皮層(iii)、湿気硬化型ホットメルトウレタン組成物の塗布厚、及び後加熱の温度を表10〜11に示す通り変更した以外は、実施例57と同様にして合成皮革を得た。
[ Reference Examples 29 to 38 ]
Hot melt urethane prepolymer (A) to be used, foaming agent composition (B), heat melting temperature of hot melt urethane prepolymer (A), skin layer (iii), coating thickness of moisture curable hot melt urethane composition, and Synthetic leather was obtained in the same manner as in Example 57 except that the post-heating temperature was changed as shown in Tables 10 to 11.
[実施例30]
ホットメルトウレタンプレポリマー(A−3)100質量部を100℃に加熱して溶融した。次いで、ポリオキシプロピレントリオール(三井化学株式会社製「MN−3050」、数平均分子量;3,000)を5質量部、N,N’−ジニトロソペンタメチレンテトラミンを2.5質量部、尿素を2.5質量部、ホウ酸を0.5質量部を混合攪拌して得た発泡剤組成物(B−6)を溶融したホットメルトウレタンプレポリマー(A−3)に2液混合撹拌機を使用して攪拌することで湿気硬化型ホットメルトウレタン組成物を得た。
次いで、得られた湿気硬化型ホットメルトウレタン組成物を前記表皮層(iii−1)上に、コンマコーターを使用して厚さ30μmとなるように塗布して、120℃で5分間加熱処理した後に、不織布を貼り合せ、その後、温度23℃、相対湿度65%の条件下で3日間放置し、中間層(ii)の厚さが50μmである合成皮革を得た。
[Example 30 ]
100 parts by mass of hot-melt urethane prepolymer (A-3) was heated to 100 ° C. and melted. Next, 5 parts by mass of polyoxypropylene triol (“MN-3050” manufactured by Mitsui Chemicals, Inc., number average molecular weight; 3,000), 2.5 parts by mass of N, N′-dinitrosopentamethylenetetramine, and urea A two-component mixing stirrer is added to a hot melt urethane prepolymer (A-3) obtained by melting a foaming agent composition (B-6) obtained by mixing and stirring 2.5 parts by mass and 0.5 parts by mass of boric acid. A moisture-curing hot melt urethane composition was obtained by using and stirring.
Next, the obtained moisture-curable hot melt urethane composition was applied on the skin layer (iii-1) so as to have a thickness of 30 μm using a comma coater, and was heat-treated at 120 ° C. for 5 minutes. Thereafter, a nonwoven fabric was bonded, and then left for 3 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a synthetic leather having a thickness of the intermediate layer (ii) of 50 μm.
[実施例31〜43、参考例39〜40]
用いるホットメルトウレタンプレポリマー(A)、発泡剤組成物(B)、ホットメルトウレタンプレポリマー(A)の加熱溶融温度、表皮層(iii)、湿気硬化型ホットメルトウレタン組成物の塗布厚、及び後加熱の温度を表11〜13に示す通り変更した以外は、実施例68と同様にして合成皮革を得た。
[Examples 31 to 43, Reference Examples 39 to 40 ]
Hot melt urethane prepolymer (A) to be used, foaming agent composition (B), heat melting temperature of hot melt urethane prepolymer (A), skin layer (iii), coating thickness of moisture curable hot melt urethane composition, and A synthetic leather was obtained in the same manner as in Example 68 except that the post-heating temperature was changed as shown in Tables 11-13.
[表6]
[Table 6]
[表7]
[Table 7]
[表8]
[Table 8]
[表9]
[Table 9]
[表10]
[Table 10]
[表11]
[Table 11]
[表12]
[Table 12]
[表13]
[Table 13]
実施例16〜29は、ポリオキシテトラメチレングリコールをポリオールの主成分として使用したホットメルトウレタンプレポリマーを用いて製造した合成皮革であるが、合成皮革の中間層の形成にDMF等の有機溶剤を一切使用せず、かつ、中間層が薄膜である場合でも良好な発泡状態を保持することができることが分かった。また、本発明の合成皮革は、風合い、耐屈曲性、及び耐加水分解性にも優れるものであった。 Examples 16 to 29 are synthetic leathers produced using a hot melt urethane prepolymer using polyoxytetramethylene glycol as the main component of polyol, but an organic solvent such as DMF is used to form an intermediate layer of the synthetic leather. It was found that a good foamed state can be maintained even when no intermediate layer is used and the intermediate layer is a thin film. In addition, the synthetic leather of the present invention was excellent in texture, flex resistance, and hydrolysis resistance.
また、実施例30〜43は、ポリカーボネートポリオールをポリオールの主成分として使用したホットメルトウレタンプレポリマーを用いて製造した合成皮革であるが、合成皮革の中間層の形成にDMF等の有機溶剤を一切使用せず、かつ、中間層が薄膜である場合でも良好な発泡状態を保持することができることが分かった。また、本発明の合成皮革は、風合い、及び耐久性にも優れるものであった。
Further, Examples 30-4 3, is a synthetic leather produced using a hot-melt urethane prepolymer using polycarbonate polyol as the main component of the polyol, an organic solvent such as DMF in the formation of an intermediate layer of a synthetic leather It was found that a good foamed state can be maintained even when no intermediate layer is used and the intermediate layer is a thin film. Further, the synthetic leather of the present invention was excellent in texture and durability.
Claims (9)
前記中間層(ii)が、請求項1〜5のいずれか1項記載の湿気硬化型ホットメルトウレタン組成物の発泡硬化物であることを特徴とする合成皮革。A synthetic leather having a base fabric (i), an intermediate layer (ii), and a skin layer (iii),
The synthetic leather, wherein the intermediate layer (ii) is a foamed cured product of the moisture-curable hot-melt urethane composition according to any one of claims 1 to 5.
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